Inverse-freezing compositions and use therof

ABSTRACT

A composite comprised of: (i) at least one inverse freezing material, and (ii) an additive in the form of at least one solid particle. Articles made of the composites, and uses of the composites or the articles incorporating same, particularly for reducing incoming shockwaves, are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.16/618,905, filed on Dec. 3, 2019, which is a National Phase of PCTPatent Application No. PCT/IL2018/050606 having International filingdate of Jun. 4, 2018, which claims the benefit of priority from IsraelPatent Applications Nos. 252660 filed on Jun. 4, 2017 and 257226 filedon Jan. 29, 2018, both entitled: “INVERSE-FREEZING COMPOSITIONS AND USETHEREOF”. The content of the above documents are incorporated byreference in their entirety as if fully set forth herein.

FIELD OF THE INVENTION

The present invention, in some embodiments thereof, relates toinverse-freezing materials, compositions comprising same, and usethereof.

BACKGROUND OF THE INVENTION

An inverse-freezing material is a material that increases its viscositywith applied heat and/or rise in temperature (upon a certain temperaturerange), without apparent loss of solvent. The increase in viscosity canbe of a few percent, or of tens or hundreds of percent. Inverse-freezingmaterials can be found in literature also under the names“inverse-melting”, “thermo-gelating”, “thermo-solidifying” and others. Afield in which inverse-freezing materials have found prolific uses isbiology and medicine, and examples for applications include injectableand controlled drug delivery systems, ophthalmic solutions andapplicators, and in situ generated implants or plugs.

Although heat reduces the armor's ability to protect the wearer/armoredobject, since all materials currently used for armors soften uponheating, and furthermore this heat might in itself damage thewearer/armored object, current-day armor has no components whichspecifically address this threat.

Furthermore, the attenuation of vibrational, mechanical, ballistic orblast-caused shocks remains a major challenge.

SUMMARY OF THE INVENTION

The present invention, in some embodiments thereof, relates tocompositions comprising inverse-freezing materials, articles comprisingsame and use thereof for impact protection or shock-wave mitigation. Insome embodiments, the compositions further compriseperformance-enhancing additives.

According to one aspect, there is provided a composite comprising aninverse freezing material, and an additive, e.g., in the form of a solidparticle. In some embodiments, the additive is present at aconcentration in the range of from 0.02% to 55%, by total weight.

According to one aspect, there is provided a composition comprising acomposite, the composite comprising (i) at least one inverse freezingmaterial, and (ii) an additive in the form of at least one solidparticle.

In some embodiments, the additive is present at a concentration of 0.5to 65%, by weight.

In some embodiments, the composition comprises at least two inversefreezing materials.

In some embodiments, the inverse freezing material is present at aconcentration of 40 to 99.9%, by weight.

In some embodiments, the composition further comprises a solvent, amatrix, or a combination thereof.

In some embodiments, the solvent comprises an aqueous solvent.

In some embodiments, the matrix comprises a fabric.

In some embodiments, the composite is characterized by undergoing one ormore from: solidification, crystallization, phase separation, gelation,or increased viscosity, upon heating or upon introduction of shock intothe composite.

In some embodiments, the composite is in the form of hydrogel.

In some embodiments, the inverse freezing material comprises a polymericcomponent selected from the group consisting of: cellulose derivatives,amphiphilic polymers, Poly succinimide, N-alkyl substituted acrylamides,Poly-4-methylpentene-1 (P4MP1),Polyethyleneoxide-polypropyleneoxide-polyethyleneoxide (PEO-PPO-PEO),poly(2-ethyl-2-oxazoline, poly(ethylene oxide)-polylactic acid blockcopolymers, and any combination thereof.

In some embodiments, the inverse freezing material comprises a smallmolecule selected from the group consisting of:4-cyano-4′-octyloxybiphenyl liquid crystal, 4-methylpyridine (4MP) withalpha cyclodextrin, nicotine, water mixtures, and any combinationthereof.

In some embodiments, the cellulose derivative is selected from the groupconsisting of: hydroxypropylcellulose, methyl cellulose, and acombination thereof.

In some embodiments, the additive is selected from the group consistingof: rubber, polystyrene, polyethylene, polypropylene, a polyvinyl,graphite, polysaccharide, polyvinyl alcohol (PVA), alginic acid,poly(methyl methacrylate) (PMMA), polyvinyl pyrrolidone, polythiophene,polylactic acid, polysuccinimide, acrylic polymer, methacrylic acidpolymers, polyamines, polyamides, peptides, polyesters, polyurethanes, abiomolecule or bio-sourced material, corn-flour (starch), starchderivatives, polyamine crosslinkers, Flubber or a derivative thereof,and any combination thereof.

In some embodiments, the additive is in the form of one or more types ofparticles, the one or more types of particles being micrometer- ornanometer-sized.

In some embodiments, the additive comprises a material selected from thegroup consisting of: diamond, graphene, ceramics, metals, metalloids,and any composition thereof.

In some embodiments, the additive is selected from the group consistingof: boron carbide (B₄C), boron nitride, silicon carbide, tungstencarbide, aluminum, alumina, silicon, silica and inorganic silicates,alkali and earth-alkali hydroxides and oxides, and any combination ormixture thereof.

In some embodiments, the composition or the composite is characterizedby an increase of flow stress of at least 10%, measured at a strainhigher than 2%, at a strain rate of 1200 l/sec to 1800 l/sec and at atemperature above the gelation or solidification point, compared to acorresponding flow stress of a pristine inverse-freezing material devoidof the additive.

In some embodiments, the composition or the composite is a shearthickening composition or composite, respectively, characterized by anincrease of viscosity of at least 20% within a shear rate range between1 l/sec and 1,000,000 l/sec, compared to a corresponding viscosity of apristine inverse-freezing material devoid of the additive.

In some embodiments, the composition or the composite is a shockattenuator, capable of reducing at least 10% of a maximal amplitude of aforce passing through 1 cm thick layer of the composition.

In some embodiments, the composition or the composite is a shockattenuator, capable of reducing at least 5% of an impulse of a forcepassing through 1 cm thick layer of the composition or the composite.

In some embodiments, the composition or the composite is capable ofreducing incoming shockwaves entering into the composition, at a valueof at least 10% higher compared to water.

In some embodiments, the composition or the composite is capable ofreducing at least 10% of the intensity of shockwaves passing thereto inthe frequencies of 0 Hz to 50,000 Hz.

In some embodiments, the gelation or solidification point is 45 to 70°C.

In some embodiments, the flow stress varies by at least |±5%|, ascompared to the flow stress of a pristine inverse-freezing materialdevoid of the PVA additive.

In some embodiments, the composition or the composite comprises aplurality of particles at a concentration of 40% to 65% weight, whereinthe composite is characterized by at least 10% shear thickening at ashear rate of at least 1 l/sec to 1000 l/sec.

According to another aspect, there is provided an article comprising thecomposition or the composite disclosed herein in an embodiment thereof,wherein the article is selected from the group consisting of protectiveshields, armors or their components, flexible armors and flexible armorcomponents, energy mitigators, personal protective gear against impactsand shocks, shock absorbers, acoustic insulators, acoustic attenuationdevices, temperature-controlled phase-change components, actuators, andtissue mimicking components.

According to another aspect, there is provided an article comprising aninverse-freezing material, wherein the article is selected from thegroup consisting of protective shields, armors or their components,flexible armors and flexible armor components, energy mitigators,personal protective gear against impacts and shocks, shock absorbers,acoustic insulators, acoustic attenuation devices,temperature-controlled phase-change component, actuators, and tissuemimicking components.

In some embodiments, the inverse-freezing material comprises aqueousmethyl cellulose.

In some embodiments, the article is characterized by an increase of flowstress of at least 10% at strains higher than 10%, upon increasing thetemperature from the gelation point to 100° C.

In some embodiments, the methyl cellulose is in the form selected fromliquid and solid, and is characterized by attenuation coefficient in therange of 0.4-0.55 Np/Cm at frequencies of 400 KHz to 1 MHz.

In some embodiments, the article comprises a first layer and an secondlayer, wherein: (i) the first layer and the second layer are heldtogether, (ii) the second layer comprises a hard material and wherein(iii) the first layer comprises the inverse freezing material or thecomposite.

In some embodiments, the hard material comprises at least one materialselected from: a metal, ceramic material, inorganic oxide, Kevlar, orultra-high molecular weight polyethylene.

In some embodiments, the first layer is an interior layer having athickness of 1 micrometer to 3 cm.

Unless otherwise defined, all technical and/or scientific terms usedherein have the same meaning as commonly understood by one of ordinaryskill in the art to which the invention pertains. Although methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of embodiments of the invention, exemplarymethods and/or materials are described below. In case of conflict, thepatent specification, including definitions, will control. In addition,the materials, methods, and examples are illustrative only and are notintended to be necessarily limiting.

BRIEF DESCRIPTION OF THE DRAWINGS

Some embodiments of the invention are herein described, by way ofexample only, with reference to the accompanying drawings. With specificreference now to the drawings in detail, it is stressed that theparticulars shown are by way of example and for purposes of illustrativediscussion of embodiments of the invention. In this regard, thedescription together with the drawings makes apparent to those skilledin the art how embodiments of the invention may be practiced.

In the drawings:

FIGS. 1A-1B illustrate an approximation to normal distribution of themeasured wave velocity at liquid state (FIG. 1A) and solid state (FIG.1B).

FIG. 2 illustrates photos of gel samples before and after compression(from left to right). Glass plates were used to reduce friction.

FIG. 3A illustrates the modified Kolsky (Split Hopkinson Bar) apparatuswith the environmental chamber, used to perform the dynamicloading/compression measurements reported herein.

FIG. 3B illustrates the methyl cellulose SG-A7C-FG methocel (A7C)hydrogel sample placed between the Klosky's bars with the Flexi-forcesensors.

FIGS. 4A-4B illustrate the curve-fitting between voltage and forcemeasured with the strain gauges (FIG. 4A) and Flexi-force sensors (FIG.4B).

FIG. 5 illustrates engineering stress-strain curves of A7C and mediumviscosity methyl cellulose (MVM, A15C methocel) hydrogels. This wasmeasured at a temperature of 80° C.

FIG. 6 illustrates engineering stress-strain curves of upper and lowerportions of methyl cellulose gel samples compared to the flow stress ofa full fresh specimen. This was measured at a temperature of 80° C.

FIG. 7 illustrates engineering stress-strain curves of A7C and MVM (typeA15C) at different concentrations of methyl cellulose and at atemperature of 80° C.

FIGS. 8 and 9 illustrate engineering stress-strain curves of A7C and MVM(type A15C) at different environmental temperatures.

FIG. 10 illustrates engineering stress-strain curves of A7C and MVM(type A15C) at different strain rates within the quasi-static loadingregime (strain rates detailed in the key).

FIG. 11 illustrates quasi static tests at strain rate of 7.5*10⁻³ sec⁻¹at 80° C. Engineering stress-strain curves of A7C and A15C, MC gels atdifferent MC concentrations. A7C solid lines, and A15C dashed lines.

FIG. 12 presents graph showing the results of quasi static tests at astrain rate of 7.5×10⁻³ sec⁻¹: engineering stress-strain curves of A7Cand A15C, MC-based hydrogels (56 gr/1) at different environmentaltemperatures. A7C is in solid lines, and A15C is in dashed lines.

FIG. 13 presents graph showing the results of quasi static tests atstrain rate 7.5*10⁻³ (l/sec). Engineering stress-strain curves of A7Csample at two different concentrations, at different environmentaltemperatures. 56 gr/l is in solid lines, and 44 gr/l is in dashed lines.

FIG. 14 illustrates typical dynamic force equilibrium for A7C gel.

FIG. 15 illustrates the dynamic compression true stress-true straincurves of A7C gel (strain rates detailed in the key).

FIG. 16 illustrates the dynamic flow curves for A7C gel comparisonbetween dynamic (black line) and quasi-static (red line) compression at80° C. (strain rates detailed in the key).

FIG. 17 illustrates engineering stress-strain curves of 4.4%, by weight,of MVM (type A15C) with and without PVA (polyvinylalcohol) (weight per 5mL solution) as additive on gel flow-stress at different concentrationsof PVA within the quasi-static loading regime at 80° C.

FIG. 18 illustrates engineering stress-strain curves of A7C with andwithout PVA as additive (0.1 g per 5 mL solution) on gel flow-stresswithin the quasi-static loading regime at 80° C.

FIG. 19 illustrates engineering stress-strain curves of A7C with andwithout different types of particles on gel flow-stress within thequasi-static loading regime at 80° C.

FIG. 20 illustrates engineering stress-strain curves of A7C with variedsizes of boron carbides particles compared to A7C alone on gelflow-stress within the quasi-static loading regime at 80° C.

FIG. 21 illustrates engineering stress-strain curves of A7C with variedconcentrations of micrometer-sized boron carbides particles (“FBC”) ongel flow-stress within the quasi-static loading regime at 80° C.

FIG. 22 illustrates the dynamic flow curves of A7C with and withoutdifferent types of particles at 70° C., and compared to thenon-composite A7C gel at quasi-static loading regime.

FIG. 23A-D illustrate: curves of: A7C gel with and without 0.3% weightof nano-meter sized boron carbides particles, compared to thenon-composite A7C gel at quasi-static compression at 70° C. (strainrates detailed in the key), and at 1500 (FIG. 23A) and 1700 sec⁻¹ at 80°C. (FIG. 23B); and Cryo-transmission electron microscopy (TEM) images ofthe nano-BC-MC composite gel, focusing on the nano-BC aggregates(hexagonal plates with a mean average diameter of 50 nm) Bar is 100 mm(FIG. 23C) or 200 nm (FIG. 23D). Examples of fibril/polymer interactionswith the aggregate are emphasized using black arrows. Two upwardpointing arrows in the lower picture show an example of free fibrils inthe gel.

FIGS. 24A-24C present graphs illustrating: the quasi-static stress flowcurves for non-composite A7C gel and a composite comprising the A7C with53% of corn-flour in water (abbreviated as STIFF) at 80° C. (FIG. 24A);the reduction of maximum force amplitudes of a 2 cm thick shearthickening fluid (FIG. 24B); the reduction of maximum force amplitudesof a 2 cm thick shear thickening inverse freezing liquid (FIG. 24C).

FIGS. 25A-25C present the one-bar and sealed cup experimental setup formechanical dynamic impact in a confined-setting measurement (FIG. 25A)and a close-up of the opened aluminum cup filled with dilute MVM (FIG.25B), liquid state (sealing O-ring also apparent).

FIG. 25C presents a photograph showing dynamic compression modifiedKolsky apparatus, with a focus on the controlled environment chamber, inwhich the gel specimen is positioned. Marked components: 1. Incidentbar; 2. Disc-shaped gel sample; 3. Transmission bar; 4. Strain gauge(one of two sets, the other on the incident bar is not shown); 5. Forcesensors leads, the sensors are positioned between the incident bar andthe gel sample, and between the gel sample and the transmission bar.

FIG. 26 presents a box-plot for energy absorption/dissipation results ofmechanical impact in confined setting measurement, for dilute (3%weight) liquid state MVM at room temperature. The red line indicatesaverage value, blue boxes enclose values within the 25 and 75percentiles, and the black line indicates extremum values.

FIG. 27 presents the temperature-dependent reflectance patterns andtimes for ultrasonic signals travelling through a medium. Top—ballisticgelatin; bottom—A7C. The red arrow indicates the gelation temperature.

FIG. 28 illustrates the comparative attenuation coefficients of MVMinverse-freezing gel, steel and water, over a frequency range of ˜400kHz to 1 MHz.

FIG. 29 illustrates the temperature-dependent attenuation coefficientvalues for A7C over a frequency range of ˜700 kHz to 1 MHz.

FIG. 30 illustrates an example for one embodiment of an article of theinvention, in which the composite (or non-composite inverse-freezingmaterial) is a component of armor. 1: a steel or other-material rigidplate, or Kevlar®. 2: A honeycomb-type layer of confined composite (ornon-composite) forming a second protective layer (against heat,shockwaves, etc.).

FIG. 31 illustrates an example for one embodiment of an article of theinvention, in which the composite (or non-composite inverse-freezingmaterial) is a component of armor. A sealed “sleeve”, flexible (andpossibly transparent—depending on the composition's components) is setaround a wearer's joint—in this case elbow, offering protection againstheat, impact, etc.

FIGS. 32A-32B present photographic images and visual description of adisclosed system in an embodiment thereof: a general structure of theexperiment system viewed from above, with some components specified(FIG. 32A), and general side view of the system, more clearly showingthe inverse-freezing material filling within its chamber (theyellow-brown conductors are those of the force-sensors) (FIG. 32B).

FIGS. 33A-33B present force amplitude graphs measured for two differentimpactor driving pressures (specified at the upper left corner in eachgraph): maximum force amplitude of 10,000N (FIG. 33A), and maximum forceamplitude of 20,000N (FIG. 33B).

FIG. 34 presents force amplitude graphs impact forces entering thelayer, in water (red) and a 10% w/w aqueous methylcellulose solution, atroom temperature.

FIGS. 35A-35B present graphs impact force mitigation of water (FIG. 35A)and a 5% w/w aqueous methylcellulose solution (FIG. 35B), at roomtemperature. A shift on the time-axis for the readings of the hindsensor (measuring the force passing through the investigated material)was performed so that both maxima have the same time value, for visualaid of the comparison of force profiles. FIG. 35A: Max. amplitude forcereduction 2.9%; impulse attenuation ˜3%; FIG. 35B: Max. amplitude forcereduction 45%; Impulse attenuation ˜40%.

FIGS. 36A-36F present graphs showing the reduction of maximum forceamplitudes of a 2 cm thick of inverse freezing fluid: 5% aq.methylcellulose solution (FIG. 36A); water (FIG. 36B); 5% ballisticgelatin solution (FIG. 36C); and 1 cm thick of: 5% aq. hydroxypropylmethylcellulose solution (FIG. 36D); compositemethylcellulose-poly(2-oxazole) (FIG. 36E); and comparing to 1 cm thickcomposite methylcellulose-nano boron carbides (FIG. 36F).

FIGS. 37A-37C present: Schematics of experiment system setup formeasurement of shock reduction by examined liquids (FIG. 37A), Forceamplitude of the striker in the experimental system (FIG. 37B); Forceamplitude in the force sensor on the incoming side of the liquid,located behind the front plate, and comparison of water and IF liquid(FIG. 37C).

FIGS. 38A-38B present graphs showing the impact force mitigation ofwater (FIG. 38A) and a 5% w/w aqueous methylcellulose solution (FIG.38B), at room temperature, by frequency. A black upwards bar marks anapproximate, theoretical “border” of frequency, at ˜20 KHz, from whichthe inverse freezing material provides complete attenuation of theimpact forces.

FIG. 39 presents graphs showing impact force mitigation of a 2 cm 10%w/w aqueous methylcellulose solution, at room temperature. A shift onthe time-axis for the readings of the hind sensor (measuring the forcepassing through the investigated material) was performed so that bothmaxima have the same time value, for visual aid of the comparison offorce profiles. Maximum amplitude force reduction: ˜80%; impulseattenuation: ˜70%.

FIG. 40 presents graphs showing impact force mitigation of a 10% w/waqueous methylcellulose solution, at room temperature, by frequency.

FIG. 41A-41B present: side view of the liquid-filled impact chamber (theimpacting bar is on the right, and advances into the chamber uponimpact) (FIG. 41A), and time-lapse pictures of: b-e: methylcellulose(AMC) 5.6% wt.; f-i: water, j-m: ballistic gelatin 5% wt. In all cases,t₀=time of impact on the liquid, sample temperature is 23±2° C. (FIG.41B).

FIG. 42 presents a graph showing gel formation by time from impact (inmicroseconds), provided by graphical analysis (brightness in arbitraryunits), as derived from the high-speed camera films.

FIG. 43 presents time-lapse pictures of AMC 5.6% wt. in a chamber withthe impact bar situated close to the rear wall. t₀=time of impact, thesample temperature is 23±2° C. and the impacting bar advances inwardsfrom the right (from left to right: 0 μsec, 66 μsec, 194 μsec, 350μsec).

Hereinabove, “A7C” refers to an A7C methyl cellulose based hydrogelhaving 5.3% weight in water.

DETAILED DESCRIPTION OF THE INVENTION

The present invention, in some embodiments thereof, relates tocompositions and composites comprising inverse-freezing materials, anduse thereof, for example, for impact protection or shock-wavemitigation.

Before explaining at least one embodiment of the invention in detail, itis to be understood that the invention is not necessarily limited in itsapplication to the details set forth in the following description orexemplified by the Examples. The invention is capable of otherembodiments or of being practiced or carried out in various ways.

The present invention is based, in part, on the inventors' findings ofsome inverse-freezing materials having one or more from: a. increasedstress flow (and therefore hardening) at quasi-staticloading/compression with heating past the gelation point (see, e.g.,FIGS. 8 and 9); b. increased stress flow (and therefore hardening) atdynamic loading/compressions and impacts compared to quasi-staticcompressions (see, e.g., FIGS. 15 and 16); c. temperature-dependentacoustic (ultrasonic wave) velocity and attenuation, the latter of whichis considerably larger than comparative materials such as steel andwater (see, e.g., FIGS. 27, 28, 29); and d. in their ambient temperature(non-heated) liquid form materials; may absorb the energy of a dynamicimpact, in a partially confined setting, hundreds of percentages betterthan water (at the same conditions).

When taking into account that the disclosed materials may undergoinverse-freezing by an endothermic transition, the inventors havecontemplated that such materials could be useful, in some embodiments,for attenuating and dispersing the energy of dynamic mechanical impacts,shockwaves, and acoustic energy—either as directly evolving from theimpacts and shockwaves or from an external source (radiated or convectedheat). In a particular non-limiting example, such materials may augmentarmors: impacts on armor surfaces (for example, by ballisticprojectiles, shrapnel, manual stabbing) may create heat that is divertedby the gelation process.

It would be advantageous to use inverse-freezing materials, in light ofthe disclosure provided herein (and specified in this section) as armorsor components in armor (a non-limiting example for two such embodimentis presented for demonstration in FIGS. 30, 31).

The shockwaves (due to dynamic impacts) are hardly attenuated bymodern-day rigid armors (such as steel plating or other hard materials)and therefore the herein disclosed materials, thanks to their largeattenuations at relatively low frequencies which are still highly potentat damage to soft tissues such as the human brain, may be employed asprotective elements for these and other shock-sensitive systems.Furthermore, since the disclosed materials, at least in someembodiments, are in their liquid state at the ambient temperatures inwhich the armor is expected to be employed (for one example, up to 65°C.), armors relying on these materials could offer increased flexibilityand shape-conformity (for example, FIG. 31) as compared to, for example,ceramic insert plates or even Kevlar®.

The present invention is further based, in part, on the finding that theperformance of the inverse-freezing materials may be enhanced bycombining various types of additives with the inverse-freezingmaterials. These findings include, for some examples, that theseadditives may confer to the new composite incorporating them one or morefrom: a. tunable stress flow in the quasi-static loading or compression,for the same additive but in different concentrations and depending onthe inverse-freezing material type: increased stress-flow (and thereforehardening) (e.g., FIG. 17) or decreased stress-flow (and thereforesoftening) (e.g., FIG. 18); b. tunable stress flow in the quasi-staticloading/compression, for different additive types (e.g., FIG. 16, 19);c. tunable stress flow in the quasi-static loading/compression, for thenon-limiting example in which the additives are rigid particles,depending on different particle sizes and concentrations (e.g., FIGS. 20and 21), and/or d. tunable stress flow in the dynamic loading orcompression (and where required, for some non-limiting examples, extremeincrease in the stress flow and therefore hardening) depending on theadditive type and concentration and in the dynamic loading orcompression and tunable sensitivity to impact or stress waves, and as aresponse to it the extent of responsive phase-transition.

Since the inventors have shown that the composite's stress-flow may betuned depending on a number of factors related to the additives (amongthese factors are, but not only, the inverse-freezing material type, theadditive's nature (for example: polymer or rigid particle), theadditive's material type (for example, metal oxide or boron carbide),the additive's size and geometry (for example, 0.7 micrometer or 55nanometer average diameters), and the additive's concentration withinthe composite, the present invention provides novel composites which, insome embodiments, are useful in a variety of applications, for examplehigher-performance armor with enhanced response to impact (for thehigher stress flow composites, whose response-strain values aresignificantly lower than the non-composite materials, and whose stressesat these values may provide better protection against the impactingobject), or for example for tissue-mimicking media, where it isdesirable to adjust the stress flow traits to approximate them asclosely as possible to the desired tissue (this may include, fornon-limiting example, an additive that lowers the stress flow). Thus,the present disclosure further provides composites of inverse-freezingmaterials and additives, the composites having enhanced performance forspecific application (e.g., impact protection would be benefitted by anincreased stress flow composite).

Furthermore, the inventors have shown that in some embodiments inversefreezing materials may solidify in response to shock. Thus,shock-induced solidification may be used as a mechanism to absorb,divest, or mitigate energies (which might otherwise be harmful to atarget).

Inverse-Freezing Materials

As used herein, the term “inverse-freezing material” (interchangeably“thermo-sensitive”, “thermo-responsive”, “thermo-gelating”,“thermo-solidifying” and/or including the prefix “reverse” to any ofthese materials), refers to a substance that is characterized byundergoing full or partial: solidification, crystallization, gelation,phase-separation or increase their viscosity, in some embodiments,without any apparent loss of solvent, upon heating and/or increasingtemperature, or, as disclosed herein upon introduction of shock waveinto the material. In some embodiments, the inverse-freezing materialundergoes at least partial solidification, gelation or crystallizationupon heating, or, as disclosed herein upon introduction of shock waveinto the material.

In some embodiments, the shock may be introduced by providing one ormore from, without limitation, vibrations, mechanical loading, manual-,ballistic- (bullet), or explosion-derived impact (shrapnel), airborneshockwaves (such as due to blast), water-, ground- or structure-conveyedshockwaves, impact due to collisions or falls, acoustic phenomena, orany combination thereof.

In some embodiments, the compositions or composite of the invention maybe in the form of one or more phases. In some embodiments, thecomposition or composite is in the form of liquid. In some embodiments,the composition or composite is in the form of gel. In some embodiments,the composition or composite is in the form of hydrogel. In someembodiments, the composition or composite is in the form of semi-solid.

As will be appreciated by one skilled in the art, the high-temperaturestate (referred to as the “solid” or “gel” state henceforth) is thusphysically different from the low-temperature state (referred to as the“liquid” state henceforth), in more than just its temperature. Thetransition between the two states does not necessarily have to be of afirst-order type (and the transition may have a continuous character).

In some embodiments, the material is in the form of gel or a hydrogel(at a certain range of temperatures). In some embodiments, the term“gel” describes a semi-solid formed from a solution, e.g., due toheating. Thus, a gel comprises a continuous liquid phase and a dispersedphase (e.g., a liquid or solid phase). In some embodiments, the term“gel” refers to hydrogel.

In some embodiments, the term “hydrogel” refers to a heterogeneous ormicro-heterogeneous composition of water and other molecules, displayingsome of the properties of a solid, including the tendency to retaintheir structure better than their liquid component alone (in this caseliquid water).

In some embodiments, the gel may be composed of aggregates of molecules(either small, polymeric, organic, inorganic, or other molecule) thatinteract with each other either directly or by mediation via otherspecies such as the solute molecules, such as, without limitation,ballistic gelatin.

In some embodiments, the gel may be composed of molecular structuresthat interact with each other within the solute (and around it), suchas, without being limited thereto, methyl cellulose hydrogels.

The gel may be composed of crystalline or semi-crystalline materials andwater, such as, without being limited thereto, the system of4-methylpyridine in alphacyclodextrin and water.

In some embodiments, the inverse-freezing material is a polymer orcopolymer, with or without the further presence of solute molecules. Insome embodiments, the inverse-freezing material comprises a smallmolecule, with or without the further presence of solute molecules (suchas, and without limitation, 4-cyano-4′-octyloxybiphenyl liquid crystal).In some embodiments, the inverse-freezing material is a combination of apolymer and small molecule.

In some embodiments, the term “polymer”, as used hereinthroughout,describes a substance, e.g., an organic substance, or an inorganicsubstance, composed of a plurality of repeating structural units(referred to interchangeably as backbone units or monomeric units),e.g., being covalently connected to one another and forming thepolymeric backbone of the polymer. The term “polymer” as used hereinencompasses organic and inorganic polymers and further encompasses oneor more of a homopolymer, a copolymer or a mixture thereof (e.g., ablend). The term “homopolymer” as used herein describes a polymer thatis made up of one type of monomeric units and hence is composed ofhomogenic back bone units. The term “copolymer” as used herein describesa polymer that is made up of more than one type of monomeric units andhence is composed of heterogenic backbone units. The heterogenicbackbone units can differ from one another by the pendant groupsthereof.

Non-limiting examples of inverse-freezing materials include cellulosederivatives, amphiphilic polymers, Polysuccinimide polymers whosesuccinimide rings have all or some been opened and linked to variousalkyl or further functionalized groups, such as but not limited toN-isopropyl, N-hexyl, N-hydroxypropyl, N-hydroxyethyl, N-hydroxyhexyl,N-alkyl substituted acrylamides (e.g., poly-N-isopropyl acrylamide[PNIPAAm], Poly-4-methylpentene-1 (P4MP1),Polyethyleneoxide-polypropyleneoxide-polyethyleneoxide (PEO-PPO-PEO),poly(ethylene oxide)-polylactic acid block copolymers, triblocks, randomor alternating thermo-responsive PEO-PPO block copolymers,poly(X-alkyl-Y-oxazoline) with X and Y being integers, or anycombinations thereof.

In some embodiments, the inverse-freezing material is one or morecellulose derivatives. In some embodiments, the cellulose derivative isselected from hydroxypropylcellulose, methyl cellulose, or anycombination thereof.

In some embodiments, the inverse-freezing material is a small molecule.Non-limiting examples of small molecule include:4-cyano-4′-octyloxybiphenyl liquid crystal, 4-methylpyridine (4MP) withalpha cyclodextrin, nicotine, and any mixture thereof.

In some embodiments, the inverse-freezing material has reverse-thermalgelation (RTG) properties. In some embodiments, the water or organicsolutions of these materials display low viscosities at low temperatures(below, at or above ambient temperature), and exhibit a sharp increaseof the viscosity as the temperature rises within a very narrowtemperature interval (known as the “gelation temperature”), producing asemi-solid gel above this interval.

In some embodiments, the inverse-freezing material is tailored todisplay substantial property changes, in response to stimuli. The“stimulus” may be mechanical stress, shockwave, chemical, physical orbiological stimuli, e.g., temperature (including external heat radiationand internal heat formation), pH, ionic strength, biochemical agents, orapplication of magnetic or electrical fields. In some embodiments, thestimulus is applied continuously; for example, the composite ismaintained at a certain temperature. In further embodiments, thestimulus is transient or is applied over a period of time sufficient totransform all or a portion of the material or composite into the desiredphysical state.

In some embodiments, the stimulus is a mechanical stress (e.g., static,quasi-static or dynamic). In some embodiments, the stimulus is a shockwave. In some embodiments, the stimulus is temperature. In someembodiments, the stimulus is heat generated due to another stimulus(such as the heat generated due to mechanical impact). In someembodiments, the stimulus may rise in pressure generated due to anotherstimulus (such as the increased pressure generated due to mechanicalimpact).

Performance-Enhancing Additives

In some embodiments, the invention provides compositions and compositescomprising inverse-freezing materials and additives. In someembodiments, the additives enhance the performance of the compositionsand composites with regard to the various applications detailed herein(e.g., impact protection or shock-wave mitigation).

As exemplified herein, a variety of additives, ranging from organicpolymers to inorganic and metallic particles, with varying geometry andsizes, have been shown to maintain the material's inverse-freezing traitas well as to affect the material's stress-flow curve and stimuliresponse.

In some embodiments, the composite comprises one or more additives.Typically, an additive is a component in a minor amount (e.g., less than60%, less than 20%, less than 10%, or less than 5%, by total weight, andany value in between) added to the composite which modifies theproperties of the composite, for example to further increase thecomposite's flow stress or to provide a feature of shear thickening tothe composite. The additive, in some embodiments, may increase thestress flow of a heated gel. In additional embodiments, the additiveenables the fine-tuning of the stress flow to suit the requirements ofcertain specific applications. As a non-limiting example, additives maybe used for tailoring the stress flow to behave similar to that of adesired tissue.

In some embodiments, the additive decreases the response time of theinverse-freezing material to undergo phase change due a stimulus.

In some embodiments, the additive facilitates the phase change of theinverse-freezing material, for example, and without being bound by anyparticular mechanism, by enabling inhomogeneous “local points”, such asbut not limited to, nucleation sites and crystallization seedingcenters, within the bulk solution of the composite.

In some embodiments, the additive is a polymeric material orcomposition. In some embodiment, the additive is a plurality ofparticles. Non-limiting examples of additives include particles ofvarying geometries, sizes and materials, such as, polyvinyl alcohol(PVA), alginic acid, Poly(methyl methacrylate) (PMMA), polyvinylpyrrolidone, starch (e.g., corn flour), starch derivatives, polyaminecrosslinkers, Flubber and its derivatives (e.g., PVA cross-lined withborax), or any combination thereof.

Further non-limiting examples of additives include a material comprisingdiamond, grapheme or graphite, polysaccharides (including e.g.,cellulose, starch, cotton), rubber (including latex), polystyrene,polyethylene, polypropylene, polyvinyls (including halogenated such aspolyvinylchlorides, and functionalized with acidic or basic groups suchas carboxylic, sulfonic, acetates and pyrrolidones), polythiophenes,polylactic acids, polysuccinimides, acrylic and methacrylic acidpolymers, polyamines and polyamides, peptides, polyesters, andpolyurethanes, or any combination thereof.

In some embodiments, the additive comprises polymers (e.g., PVA) havingan average molecular weights that varies by at least 1%, at least 5%,least 10%, at least 15%, least 20%, or at least 25%.

In some embodiments, the additive is selected from: ceramics, metals(e.g., aluminum, silica), metalloids, alumina, or a composition or amixture thereof.

In some embodiments, the additives are nano-metered sized (for example,nano-meter diameter) particles selected from metals, metalloids, andceramics. As used herein and in the art the term “metalloid” refers to achemical element having both metals and nonmetals properties. In someembodiments, the metalloid is selected from, but not limited to: boron,silicon, germanium, arsenic, antimony, and tellurium.

In exemplary embodiments, the additive is boron carbide (B₄C).

In some embodiments, the additive particle may have geometry or a formselected from, but is not limited to: colloidal, spherical, cubic,plate, rod, wire, toroidal, or ring, fibrillar, dendritic (fractal),brush, or amorphous.

Reference is made to FIG. 23 showing that a composite comprisingnanoparticles of boron carbide and A7C methyl cellulose displays, underdynamic loading or compression, an increase of its flow-stress by 2400%at a strain of 1% up to an increase of 44700% at a strain of 6%, incomparison to the non-composite A7C submitted to the same dynamiccompression. Some embodiments of composites in which the additives werealumina spheres and alumina wires also showed increased stress flow,compared to the non-composite A7C methyl cellulose hydrogel, underdynamic loading/compression (FIG. 22).

In exemplary embodiments, the additive is micrometer-sized (e.g., havingan average diameter of about 0.7 micrometers). In additional exemplaryembodiments, the additive is nano-sized (e.g., in the form ofnanoparticle(s), with an average diameter of about 55 nm).

Hereinthroughout, the term “nanoparticle” describes a particle featuringa size of at least one dimension thereof (e.g., diameter, length,thickness) that ranges from about 1 nanometer to 1000 nanometers.

In some embodiments, the size of the particle described hereinrepresents an average size of a plurality of nanoparticles. In someembodiments, the average size (e.g., diameter, length) ranges from about1 nanometer to 500 nanometers. In some embodiments, the average sizeranges from about 1 nanometer to about 300 nanometers. In someembodiments, the average size ranges from about 1 nanometer to about 200nanometers. In some embodiments, the average size ranges from about 1nanometer to about 100 nanometers. In some embodiments, the average sizeranges from about 1 nanometer to about 55 nanometers. In someembodiments, the average size ranges from about 1 nanometer to 50nanometers. In some embodiments, the average size ranges from about 20nanometer to about 500 nanometers. In some embodiments, the average sizeranges from about 20 nanometer to about 200 nanometers, and in someembodiments, it is lower than 500 nm.

The particle can be generally shaped as a sphere, a rod, a wire, aplate, a rhombohedral, a cylinder, a ribbon, a sponge, and any othershape, or can be in a form of a cluster of any of these shapes, or cancomprises a mixture of one or more shapes.

In some embodiments, the plurality of particles is at a concentration ofat least 0.01, at least 0.05, at least 0.1, at least 0.2, at least 0.3,at least 0.4, at least 0.5, at least 1, at least 2, at least 5, at least10, at least 15, at least 30, at least 50, at least 100, at least 500,at least 600 milligrams per ml of the material or any valuetherebetween. In some embodiments, the plurality of additive is at aconcentration of at most 1, at most 3, at most 5, at most 8, at most 9,at most 10, at most 11, at most 12, at most 13, at most 15, at most 30,at most 50, at most 100, at most 200, at most 500, or at most 600milligrams per ml of the material or any value therebetween.

The additive may comprise a plurality of particles conferring to thecomposite further features of shear thickening, so that it behaves undermechanical stimuli (such as dynamic loading, compression, impact, and/orshock) and other stimuli (such as shockwaves) as a shear thickeningfluid. Shear Thickening Fluids (STFs) are Non-Newtonian Fluids thatchange their viscosity with changing shear rates. In some shear rateranges (usually defined as being above the critical shear rate), theviscosity increases with increasing shear rates. Thus, these fluids canrespond to mechanical impacts (ranging from falling objects and handpunches to stabbing and ballistic projectiles). There are a variety ofmaterials that show shear thickening properties, including but notlimited to “oobleck” (a solution of starch in water with a large weightpercentages, around 50-60%, of the starch). The starch provides theshear-thickening enabling particles, but these can be also syntheticparticles, such as silica nanoparticles, and the solution can benon-aqueous, such as ethylene glycol.

As exemplified herein below, addition of a thermally-responsivecomponent, which both endothermically converts to the “solid” state(thus, e.g., taking up some of the energy of the impact) and hardens dueto this heat (thus, e.g., enabling better spread of the energy acrossthe armor and lessening the impact's harm toward the wearer orarmor-protected object). A non-limiting exemplary embodiment combingboth components, of STF and of inverse-freezing (referred to hereon asSTIFF—shear thickening inverse freezing fluid) is composed of 53% weightcorn-flour additive, 5.3% weight A7C-type methyl cellulose, in anaqueous solution. This exemplary embodiment may be prepared and measuredfor both the behavior of an inverse-freezing material, which it doesindeed show by stiffening upon heating, and for its mechanical behavioras measured by quasi-static loading/compression. As demonstrated herein,the exemplified STIFF showed a stress flow curve similar to that of thenon-composite A7C methyl cellulose hydrogel (FIGS. 24A-C). However,STIFF-type materials show reduction of shockwaves forces that is muchgreater than those of STF alone. This embodiment demonstrates harnessingboth the thermal-responsive capability of inverse freezing fluids whichhas been shown to mitigate shockwave forces and the kineticimpact-induced hardening.

The Composites

According to another aspect, there is provided a composite comprising aninverse-freezing material and an additive at a concentration in therange of from 0.02 to 80% (e.g., 0.02%, 0.05%, 1%, 5%, 10%, 15%, 20%,25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 70%, or 80% by total weight,including any value and range therebetween).

In some embodiments, the additive comprises a solid material. In someembodiments, the additive comprises one or more solid particles.

In some embodiments, the inverse freezing material is present at aconcentration of 40 to 99.9%, 50 to 99.9%, 60 to 99.9%, or 40 to 95%, byweight of the composite.

In some embodiments, the additive is incorporated within theinverse-freezing material. In some embodiments, the additive isdispersed within the inverse-freezing material.

According to another aspect, there is provided a composition comprisingthe composite in an embodiment thereof. In some embodiments, thecomposition further comprises a solvent, a matrix, or a combinationthereof. In some embodiments, the solvent comprises an aqueous solvent.In some embodiments, the matrix comprises a fabric. In some embodiments,solvent may contain inorganic cations or anions, organic solvent (suchas but no limited to alcohol, ketone, aldehyde, ester, amide, ether)and/or an aqueous solution. In some embodiments, the matrix comprises afabric or a flexible or non-flexible scaffold, a gel (e.g., a hydrogel)or any combination thereof.

The term “composite” is used herein to denote a composition made of atleast two substances (e.g., materials and additives). In someembodiments, the two or more substances have different characteristics,wherein each substance, retains, at least partially, its identity whilecontributing desirable properties to the whole.

In some embodiments, the composite is characterized by a first physicalstate at a temperature below gelation temperature (e.g., 45° C., 55° C.,65° C. or 75° C., including any value and range therebetween).

Herein, by “first physical state” it is meant to refer to the liquidstate. The term “second physical state” generally refers to the solidstate (as defined above, for inverse-freezing materials). In someembodiments, this solid state has a flow stress of at least 10 KPa atstrains of 20% in quasi-static loading/compression.

In some embodiments, the flow stress of the second physical state ischaracterized by at least 10, at least 15, at least 20, at least 25, atleast 30, at least 35 or at least 40 KPa, including any valuetherebetween, and at a strain of at least 20%.

In some embodiments, the composite may convert to the second physicalstate (e.g., solid state) at the solidification temperature, known asgelation temperature in the cases where the second physical state is agel, or due to other stimuli, such as mechanical impact or introductionof shockwaves into the material. The gelation temperature, and/or thesensitivity to impact or shockwave stimuli may be tunable for someinverse-freezing materials and their composites. In some embodiments,this tuning depends on a number of factors, among which for non-limitingexample are: the component's concentrations, the presence of additives,the heating rate, and the extent of the interface of theinverse-freezing material with the shock-conveying element.

In some embodiments, the composite is characterized by gelationtemperature, 45° C., 50° C., 55° C., or 65° C., and anywhere in therange between these values.

In some embodiments, the composite is characterized by undergoingsolidification, crystallization, phase separation or gelation, partiallyor fully, and/or increased viscosity without apparent loss of solvent,upon increase in temperature and/or heating.

In some embodiments, the additive (e.g., B₄C nanoparticles) increasesthe flow stress by at least 1000% at a strain of 1% when tested bydynamic loading (e.g., shock, high rate compression, etc.) at atemperature above 65° C. and a strain rates of 1200-1700 l/sec (e.g.,1500l/sec). In some embodiments, the additive increases the flow stressby at least 2000% at a strain of 1% when tested by dynamic loading(e.g., shock) at a temperature above 65° C. and strain rates of1200-1700 l/sec (e.g., 1500l/sec). In some embodiments, the additiveincreases the flow stress by at least 10,000% at a strain of 1% whentested by dynamic loading (e.g., shock) at a temperature above 65° C.and a strain rates of 1200-1700 l/sec (e.g., 1500l/sec). In someembodiments, the additive increases the flow stress by at least 30,000%at a strain of 1% when tested by dynamic loading (e.g., shock) at atemperature above 65° C. and strain rates of 1200-1700 l/sec (e.g., 1500l/sec). In exemplary embodiments, the B₄C nanoparticles increase theflow stress of the methyl cellulose composite by 1000% at a strain of 2%up to an increase of 32000% at a strain of 6% when tested by dynamicloading (e.g., fast impact at 70° C. and a strain rate of 1500 l/sec).

In some embodiments, the liquid and solid methyl cellulose arecharacterized by attenuation coefficient of at least 0.01 Np/Cm atfrequencies of 400 KHz to 1 MHz. In some embodiments, the liquid andsolid methyl cellulose are characterized by attenuation coefficient ofat least 0.2 Np/Cm at frequencies of 400 KHz to 1 MHz. In someembodiments, the liquid and solid methyl cellulose are characterized byattenuation coefficient of at least 0.4 Np/Cm at frequencies of 400 KHzto 1 MHz. In exemplary embodiments, the liquid and solid methylcellulose are characterized by attenuation coefficient in the range of0.4-0.55 Np/Cm at frequencies of 400 KHz to 1 MHz.

In some embodiments, the article comprises inverse-freezing materialswith an adjusted composition for acoustic insulation of ears, orsensitive acoustic instruments.

As exemplified in the Examples section below, the inverse-freezingmaterials (e.g., methyl cellulose solution) have been shown to providesignificant (e.g., at least 90%, or even complete) attenuation ofshockwaves at various frequencies.

In some embodiments, the inverse-freezing material, the composite or thecomposition (e.g., methyl cellulose and its composites) shows asignificant ability to reduce shockwave forces, as measured by themaximal amplitude of force, passing therethrough. When compared to watertested under the same conditions (identical apparatus, temperature, andthickness) these inverse-freezing materials show, in some embodiments,improved reduction of the shockwaves, mitigating at least 1.5 times moreenergy per cm thickness than water. In some embodiments, theinverse-freezing material, the composite or the composition (e.g.,methyl cellulose hydrogel) is characterized by mitigation of at least 20times more energy per cm thickness than water tested under the sameconditions (identical apparatus, temperature, and thickness). This wasexemplified by water attenuating 3% of the maximal amplitude ofshockwave forces with the inverse-freezing solution attenuating morethan 70% of the maximal amplitude of shockwave forces.

In some embodiments, the composition or the composite is capable ofattenuating shockwaves, by reduction of: at least 5%, at least 10%, orat least 15%, of the maximal amplitude of forces passing through 1 cmthick layer of the composition.

In some embodiments, the composition or the composite is capable ofattenuating shockwaves, by reduction of: at least 5%, at least 10%, orat least 15%, of the impulse of force of forces passing through 1 cmthick layer of the composition or composite.

In some embodiments, the composition or the composite is capable ofattenuating incoming shockwaves entering into the composition, by areduction of at least 5%, at least 10%, or at least 15% higher, comparedto a reference material. In some embodiments the reference material iswater or a material with the same acoustic impedance. In someembodiments, the composition or the composite is capable of reducingincoming shockwaves entering into the composition, by at least 5%, or atleast 10% higher reduction compared to water.

In some embodiments, the composite or the composition is characterizedby its ability to attenuate shockwaves, so that within the range offrequencies of 0 Hz to 50,000 Hz a reduction of at least 5%, at least10%, or at least 15% of the intensity of the waves occurs.

The shockwaves nay then be further attenuated due to passage within thecomposite or the composition, as detailed herein.

In some embodiments, the flow stress of the inverse-freezing material(e.g., methyl cellulose hydrogel) is increased by at least 100% at atemperature above 65° C., as compared to the flow stress of the inversefreezing material not comprising the additive. In exemplary embodiments,the flow stress of methyl cellulose is increased by at least 300% at atemperature above 65° C. as compared to the flow stress of the inversefreezing material not comprising the additive. In exemplary embodiments,the flow stress of methyl cellulose is increased by at least 500% at atemperature above 65° C. as compared to the flow stress of the inversefreezing material not comprising the additive.

In some embodiments, the ultrasonic wave velocity of theinverse-freezing material (e.g., methyl cellulose) is increased by atleast 100 m/sec when the temperature rises from 14° C. to 80° C. In someembodiments, the ultrasonic wave velocity of the inverse-freezing isincreased by at least 100 m/sec when the temperature rises from 14° C.to 80° C.

In these embodiments, an element is achieved in which temperaturechanges enable to tailor the element's acoustic performance.

In some embodiments, the flow stress of the inverse-freezing material(e.g., methyl cellulose hydrogel) is increased by at least 5% at strainshigher than 10%, when the temperature increases from e.g., 65° C. to100° C. In some embodiments, the flow stress of the inverse-freezingmaterial is increased by at least 10% at strains higher than 10%, whenthe temperature increases from e.g., 65° C. to 100° C. In someembodiments, the flow stress of the inverse-freezing material isincreased by at least 50% at strains higher than 10%, when thetemperature increases from e.g., 65° C. to 100° C. In exemplaryembodiments, the methyl cellulose is characterized by an increase offlow stress by at least 100% at strains higher than 10%, when thetemperature increases from e.g., 65° C. to 100° C.

In some embodiments, the flow stress of methyl cellulose hydrogel isincreased by at least 200% at a temperature ranging from 65° C. to 100°C., compared to lower temperature.

In some embodiments, the flow stress of the inverse-freezing material(e.g., methyl cellulose hydrogel) is increased by at least 2 folds at atemperature above 65° C. and at a strain rate above 10³ l/sec comparedto lower compression rates. In some embodiments, the flow stress of theinverse-freezing material is increased by at least 5 folds at atemperature above 65° C. and at a strain rate above 10³ l/sec comparedto lower compression rates. In exemplary embodiments, the flow stress ofthe methyl cellulose is increased by at least 10 folds at a temperatureabove 65° C. and at a strain rate above 10³ l/sec compared toquasi-static compression rates.

In some embodiments, the flow stress of the inverse-freezing material(e.g., methyl cellulose) is increased by at least 100% at a strain of4.5%, when dynamic compression was measured at a temperature above 65°C. compared to quasi-static loading. In some embodiments, the flowstress of the inverse-freezing material is increased by at least 300% ata strain of 4.5%, when dynamic compression was measured at a temperatureabove 65° C. compared to quasi-static loading. In exemplary embodiments,the flow stress of the methyl cellulose is increased by at least 600% ata strain of 4.5%, when dynamic compression was measured at a temperatureabove 65° C. compared to quasi-static loading. In some embodiments, theflow stress of the inverse-freezing material is increased by at least500% at a strain of 15%, when dynamic compression was measured at atemperature above 65° C. compared to quasi-static loading. In someembodiments, the flow stress of the inverse-freezing material isincreased by at least 1000% at a strain of 15%, when dynamic compressionwas measured at a temperature above 65° C. compared to quasi-staticloading. In some embodiments, the flow stress of the inverse-freezingmaterial is increased by at least 1500% at a strain of 15%, when dynamiccompression was measured at a temperature above 65° C. compared toquasi-static loading. In exemplary embodiments, the flow stress of themethyl cellulose is increased by at least 1800% at a strain of 15%, whendynamic compression was measured at a temperature above 65° C. comparedto quasi-static loading.

In some embodiments, the flow stress of the inverse-freezing material isincreased by at least 250% upon strain ranging between 10-50%, whenincreasing the concentration from 28 to 224 gr/l at 80° C. In someembodiments, the flow stress of the inverse-freezing material isincreased by at least 45% upon strain ranging between 10-50%, whenincreasing the concentration from 28 to 224 gr/l at 80° C. In someembodiments, the flow stress of the inverse-freezing material isincreased by at least 75% upon strain ranging between 10-50%, whenincreasing the concentration from 28 to 224 gr/l at 80° C. In exemplaryembodiments, the flow stress of the methyl cellulose is increased by atleast 45-75% upon strain ranging between 10-50%, when increasing theconcentration from 28 to 224 gr/l at 80° C.

In some embodiments, the composite is characterized by at least 5%decrease as compared to the flow stress of the inverse freezing materialnot comprising an additive. In exemplary embodiments, the composite ischaracterized by at least 10% decrease as compared to the flow stress ofthe inverse freezing material not comprising an additive. In someembodiments, the composite is characterized by at least 5% decrease ascompared to the flow stress of the inverse freezing material notcomprising PVA additive. In exemplary embodiments, the composite ischaracterized by at least 10% decrease as compared to the flow stress ofthe inverse freezing material not comprising PVA additive.

In some embodiments, the composite may be homogeneous in space or mayconsist of different zones displaying different densities and/or otherproperties.

By “different zones” it is meant to refer to e.g., nanometric, up tomacroscopic, continuous or discontinuous, creating independent orinterconnected domains within the composite, having several geometries,architectures and spatial arrays, dispersed homogeneously orheterogeneously, isotropically or not.

In some embodiments, the additive concentration ranges from about 0.01to 10 milligrams per ml of the material (e.g., the composite). In someembodiments, the additive concentration ranges from about 0.05 to 10milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 0.1 to 10 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 0.2 to 10 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 0.3 to 10 milligrams per mlof the material. In some embodiments, the additive concentration rangesfrom about 0.4 to 10 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 0.5 to 10milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 1 to 10 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 2 to 10 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 0.01 to 8 milligrams per mlof the material. In some embodiments, the additive concentration rangesfrom about 0.05 to 8 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 0.1 to 8milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 0.2 to 8 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 0.3 to 8 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 0.4 to 8 milligrams per mlof the material. In some embodiments, the additive concentration rangesfrom about 0.5 to 8 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 1 to 8milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 2 to 8 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 0.01 to 12 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 0.05 to 12 milligrams perml of the material. In some embodiments, the additive concentrationranges from about 0.1 to 12 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 0.2 to 12milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 0.3 to 12 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 0.4 to 12 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 0.5 to 12 milligrams per mlof the material. In some embodiments, the additive concentration rangesfrom about 1 to 12 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 2 to 12milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 0.01 to 15 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 0.05 to 15 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 0.1 to 15 milligrams per mlof the material. In some embodiments, the additive concentration rangesfrom about 0.2 to 15 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 0.3 to 15milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 0.4 to 15 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 0.5 to 15 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 1 to 15 milligrams per mlof the material. In some embodiments, the additive concentration rangesfrom about 2 to 15 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 0.01 to 30milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 0.05 to 30 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 0.1 to 30 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 0.2 to 30 milligrams per mlof the material. In some embodiments, the additive concentration rangesfrom about 0.3 to 30 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 0.4 to 30milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 0.5 to 30 milligrams per ml of thematerial. In some embodiments, the additive concentration ranges fromabout 1 to 30 milligrams per ml of the material. In some embodiments,the additive concentration ranges from about 2 to 30 milligrams per mlof the material. In some embodiments, the additive concentration rangesfrom about 1 to 50 milligrams per ml of the material. In someembodiments, the additive concentration ranges from about 1 to 100milligrams per ml of the material. In some embodiments, the additiveconcentration ranges from about 1 to 600 milligrams per ml of thematerial.

In some embodiments, the composite comprises an additive is in the formof millimeter sized, microsized or nanosized particles at e.g., 20% to70% weight, at e.g., 30% to 70% weight, at e.g., 20% to 65% weight, ate.g., 30% to 60% weight, or at e.g., 40% to 65% weight, including anyvalue and range therebetween.

In some embodiments, the composite has a shear thickening inversefreezing fluid characterized by an increase of at least 10%, or at least20% viscosity at a shear rate of at least 1 l/sec, least 10 l/sec, atleast 50 l/sec, at least 100 l/sec, at least 500 l/sec, at least 1000sec⁻¹, at least 5000 l/sec, at least 10,000 l/sec, at least 50,000l/sec, at least 100,000 l/sec, at least 500,000 l/sec, or at least1,000,000 l/sec, including any value and range therebetween.

In some embodiments, the composite is characterized by an increase of atleast 50% in viscosity at a shear rate of at least 1 l/sec, at least 10l/sec, at least 50 l/sec, at least 100 l/sec, at least 500 l/sec, atleast 1000 sec⁻¹, at least 5000 l/sec, at least 10,000 l/sec, at least50,000 l/sec, at least 100,000 l/sec, at least 500,000 l/sec, at least1,000,000 l/sec, including any value and range therebetween. In someembodiments, the composite is characterized by an increase of at leastten times in viscosity at at least 1 l/sec, at least 10 l/sec, at least50 l/sec, at least 100 l/sec, at least 500 l/sec, at least 1000 sec⁻¹,at least 5000 l/sec, at least 10,000 l/sec, at least 50,000 l/sec, atleast 100,000 l/sec, at least 500,000 l/sec, at least 1,000,000 l/sec,including any value and range therebetween. Herein, by “increase” it ismeant to refer to the composite, or composition, compared to theinverse-freezing material not comprising the additive.

The Articles

The present inventors have contemplated that an inverse freezingmaterial may be utilized as a second (e.g., inner) layer of a structure(e.g., an armor), behind a first (e.g., outer) layer. The first layermay comprise, for example, elements that allow to stop or hinder bulletsor hard-bodied objects from penetrating the armor. The inverse freezingmaterials in the second layer may allow to mitigate shockwaves andforces that the impact produces, and thus protect the wearer or target,such as a building or sensitive components within a system, from theshocks' damaging effects.

The shape of the layers may be but is not limited to that of plates,flexible sheet-like, interwoven ribbons or fibers, or intermixed as amulti-component bulk (such as particles of the hard material within theinverse-freezing material or composite).

According to an aspect of some embodiments of the present invention,there is provided an article comprising inverse-freezing material e.g.,a solution of any cellulose derivative as disclosed herein (e.g., methylcellulose solution).

In some embodiments, the armor is protective clothing, benefiting fromthe fluidity of the inverse-freezing materials.

In some embodiments, by “cellulose derivative” it is also meant toencompass cellulose (e.g., methyl cellulose) solution. In someembodiments, by “solution” it is meant to refer to an aqueous solution.In some embodiments, by “cellulose solution” it is meant to refer to 1%to 40%, 1% to 30%, 5% to 20%, or 1% to 10%, by weight, cellulose,including any value and range therebetween.

In some embodiments, by “cellulose solution” it is meant to refer to 1%,5%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%, by weight, cellulose (e.g.,methyl cellulose) including any value and range therebetween.

In exemplary embodiments, the cellulose solution comprises about 5%, byweight, methyl cellulose.

In additional exemplary embodiments, the cellulose solution comprisesabout 10%, by weight, methyl cellulose.

In some embodiments, the article is a ballistics protection apparatus.In some embodiments, the article is a ballistics-grade article. In someembodiments, the article is a bullet proof vest. In some embodiments,the article is an armor (e.g., body armor) or a shield. In someembodiments, the article is configured to absorb and dissipate theenergy from projectiles, percussion waves, shock waves or heat sources.In some embodiments, the shockwaves and heat can also be sourced to anarticle comprising blast, e.g., an exploding material.

In some embodiments, the article (e.g., in the form of a bullet proofvest, ballistics, shrapnel, or shock protective layer) comprises atleast two layers: an inner (also referred to as: “interior”) layer andan outer layer. Herein by “inner layer and an outer layer” it is alsomeant to refer to “front plate, and back (or rear) plate”, or to “frontpanel and back (or rear) panel”, respectively.

In some embodiments, the front and rear panels may be coupled togetherby any suitable means, such as welding, bonding, or mechanicallyfastening. In one embodiment, the front and rear panels are seam weldedtogether along their respective peripheries.

In some embodiments, the inner layer comprises inverse-freezingmaterial, for example, cellulose (“cellulose layer”).

In some embodiments, the inner layer further comprises an additive, forexample in the form of one or more types of particles as disclosedhereinthroughout.

In some embodiments, the types of particles may be characterized bydifferent sizes thereof (e.g., 50% or more different in size).

In some embodiments, the inner layer comprising inverse-freezingmaterial (such as 5% weight methylcellulose aqueous solution) has athickness of 0.1, 0.5, 1, 1.5, 2, 2.5, or 3 cm, including any value andrange therebetween, although it will be appreciated that the layers mayhave any other suitable thickness.

In some embodiments, the inverse-freezing material (e.g., cellulose)layer is configured to absorb and dissipate the energy from projectiles,pressure waves (e.g., explosive device), shock wave, or heat sourcesreaching thereto. In some embodiments, the inverse-freezing material(e.g., cellulose) layer allows to absorb forces or shock waves reachingthe inner layer.

In some embodiments, by “absorb” it is meant to reduction of e.g., 10%,20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, or even 100%, including anyvalue therebetween, of the maximum amplitude of the force (impact force)signal incoming into the inner (e.g., cellulose) layer after the forcesignal passes through and exits the inner (e.g., cellulose) layer.

In some embodiments, by “reduction” it is meant to refer to % reductionper 1 cm of the inverse-freezing material layer.

In some embodiments, the inner layer comprising cellulose has athickness of 0.1, 0.5, 1, 1.5, 2, 2.5, or 3 cm, including any value andrange therebetween, and the cellulose solution comprises 5%, 6%, 7%, 8%,9%, 10%, 15%, 20%, 25%, 30%, 35%, or 40%, by weight, cellulose,including any value and range therebetween.

In some embodiments, the inner layer comprising cellulose has athickness of 10 nm, 100 nm, 500 nm, 1 micrometer, 10 micrometer, 100micrometer, 1 mm, 5 mm including any value and range therebetween, andthe cellulose solution comprises 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%,30%, 35%, or 40%, by weight, cellulose, including any value and rangetherebetween.

In exemplary embodiments, the inner layer comprising cellulose has athickness of about 1 cm, or about 2 cm, and the cellulose solutioncomprises about 5%, by weight, cellulose, including any value and rangetherebetween.

In exemplary embodiments, the inner layer comprising cellulose has athickness of about 2 cm, and the cellulose solution comprises about 10%,by weight, cellulose, including any value and range therebetween.

Herein by “force” it is also meant to encompass kinetic impact forces,and shockwaves.

In some embodiments, the cellulose layer allows to reduce the thicknessof the outer layer (e.g., ceramic layer) by at least 10%, at least 20%,at least 30%, at least 40%, or at least 50%.

Herein by “allows to reduce the thickness” it is meant that thethickness of the outer layer may be reduced while maintaining the sameabsorbance the impact shock, compared to a situation lacking thepresence of the inner layer.

It will be appreciated, however, that the present invention is notlimited to the dimensions recited herein, and any other suitabledimensions may be selected based upon the size of the user and thedesired coverage area.

Furthermore, even without reduction in thickness of the outer layer, itwill be appreciated that the advantage to the wearer/protected target issuch that it is better protected against impacts and shocks due to thepresence of the second layer.

In some embodiments, the presence of an inverse-freezing component in ashear-thickening fluid provides this composite with increased ability tomitigate shocks and impact forces, compared to the shear-thickeningfluids without this additional component.

In an exemplary embodiment, methyl cellulose was introduced into anaqueous cornstarch solution, which may be shear thickening. The aqueouscornstarch solution without the methylcellulose shows 2-8% reduction ofmaximum amplitude of forces, but the inverse-freezing compositesolution, comprising aqueous cornstarch and methylcellulose shows 56%reduction of the maximum amplitude of forces.

In some embodiments, the article comprising cellulose is characterizedby a first physical state below the methyl cellulose's hydrogel'sgelation point (e.g., within the range of 20−80° C., 20 to 70° C., 40 to70° C., or 45 to 70° C.).

In some embodiments, the article comprising methyl cellulose ischaracterized by a second physical state above the hydrogel's gelationpoint.

In some embodiments, the second physical state has characteristics of asolid (gel), such as flow stress of at least 1 KPa, or, in someembodiments, at least 10 KPa, at a strain of 0.5%.

According to another aspect of some embodiments of the present inventionthere is provided an article comprising the composite disclosed herein.

In some embodiments, the article is characterized by an increase of flowstress by at least 1%, at least 5%, or by at least 10% at strains higherthan 10%, when the temperature increases from the gelation temperatureto 100° C.

In some embodiments, the article is characterized by an increase of flowstress of at least 45%, at least 50%, at least 55%, at least 60%, atleast 65%, at least 70%, or at least 75%, when increasing theconcentration of inverse-freezing component, e.g. methyl cellulose from28 to 56 gr/l at 80° C.

In some embodiments, the ultrasonic wave velocity of the article isincreased by at least 100 m/sec when the temperature rises from 14° C.to 80° C. In some embodiments, the ultrasonic wave velocity of thearticle is increased by at least 160 m/sec when the temperature risesfrom 14° C. to 80° C. In some embodiments, the ultrasonic wave velocityof the article is increased by at least 170 m/sec when the temperaturerises from 14° C. to 80° C.

In some embodiments, the article is characterized by an increase of flowstress by at least 10%, at least 50%, at least 100%, at least 200%, atleast 300%, at least 400%, or at least 500%, at strains above 4% at astrain rate above 10³ l/sec, compared to the flow stress at the samestrains at strain rates below 1 l/sec, at a temperature above thegelation or solidification temperature.

In some embodiments, the article is characterized by an increase of flowstress by at least 100% at a strain of 4.5% under dynamic loading orcompression at a temperature above the gelation or the solidificationtemperature compared to quasi-static loading or compression. In someembodiments, the article is characterized by an increase of flow stressby at least 200% at a strain of 4.5% under dynamic loading orcompression at a temperature above the gelation or the solidificationtemperature compared to quasi-static loading or compression. In someembodiments, the article is characterized by an increase of flow stressby at least 300% at a strain of 4.5% under dynamic loading orcompression at a temperature above the gelation or the solidificationtemperature compared to quasi-static loading or compression. In someembodiments, the article is characterized by an increase of flow stressby at least 400% at a strain of 4.5% under dynamic loading orcompression at a temperature above the gelation or the solidificationtemperature compared to quasi-static loading or compression. In someembodiments, the article is characterized by an increase of flow stressby at least 500% at a strain of 4.5% under dynamic loading orcompression at a temperature above the gelation or the solidificationtemperature compared to quasi-static loading or compression.

In some embodiments, the article is characterized by an increase of flowstress by at least 500%, at least 600%, at least 700%, at least 800%, atleast 900%, at least 1000%, at least 1100%, at least 1200%, at least1300%, at least 1400%, at least 1500%, at least 1600%, at least 1700%,or at least 1800%, at a strain of 15% under dynamic loading orcompression, at gelation or solidification temperature compared toquasi-static loading or compression.

In some embodiments, the article is characterized by attenuationcoefficient of at least 0.01 Np/Cm at frequencies of 400 KHz to 1 MHz.In some embodiments, the article is characterized by attenuationcoefficient of at least 0.2 Np/Cm at frequencies of 400 KHz to 1 MHz. Insome embodiments, the article is characterized by attenuationcoefficient of at least 0.4 Np/Cm at frequencies of 400 KHz to 1 MHz. Insome embodiments, the article is characterized by attenuationcoefficient in the range of 0.4 to 0.55 Np/Cm at frequencies of 400 KHzto 1 MHz. In some embodiments, the article is characterized byattenuation coefficient in the range of 0.4 to 0.5 Np/Cm at frequenciesof 400 KHz to 1 MHz.

In some embodiments, the article is characterized by significantreduction of shockwaves in a certain range of frequencies. In someembodiments, the article is characterized by near-complete reduction (toapproximately zero value) in a certain range of frequencies.

In some embodiments, the article comprises a body armor wherein thearmor is in the form of an interior layer and an outer layer. In someembodiments, the interior layer and the outer layer are bonded together.In some embodiments, the outer layer comprises a hard plate. In someembodiments, the interior layer comprises an inverse freezing material.

In some embodiments, the article has an interior layer comprising anadditive at a concentration of 0.02% to 55%, by total weight of theinverse freezing material and the additive.

In some embodiments, the article has an interior layer comprising anadditive at a concentration of 0.1% to 55%, by total weight of theinverse freezing material and the additive. In some embodiments, thearticle has an interior layer comprising an additive at a concentrationof 1% to 50%, by total weight of the inverse freezing material and theadditive. In some embodiments, the article has an interior layercomprising an additive at a concentration of 5% to 40%, by total weightof the inverse freezing material and the additive.

In some embodiments, the hard material (e.g., in the form of a plate)comprise a ceramic material. In some embodiments, the hard materialcomprises one or more from: metal, inorganic oxide, Kevlar, orultra-high molecular weight polyethylene. In some embodiments, the hardplate has a thickness of 1 to 100 mm, or 1 to 10 mm.

In some embodiments, the interior layer has a thickness of 0.1 to 10 cm.In some embodiments, the interior layer has a thickness of 0.5 to 5 cm.In some embodiments, the interior layer has a thickness of 1 micrometerto 5 cm, e.g., 1 micrometer, 1 mm, 0.5 cm, 1 cm, 2 cm, 3 cm, 4, or 5 cm,including any value and range therebetween. In some embodiments, theinterior layer has a thickness of less than 1 micrometer, e.g., 100 to900 nm.

Thus, according to another aspect of embodiments of the invention, thereis provided a kit comprising any of the cellulose derivative or thecomposites discloses herein.

Any article that may benefit from the enhanced mechanical property(e.g., the flow stress) of the composite or inverse-freezing material(e.g., methyl cellulose hydrogel) or its energy absorption/dispersionproperties (such as ultrasonic wave attenuation or other frequencieswhich are harmful to the target and are generated by shockwaves)described herein is contemplated.

Exemplary articles include, but are not limited to, an acousticinsulator, acoustic attenuation, an article for military use, an articlefor security use, a protective shield, flexible armor and flexible armorcomponents, energy mitigators, personal protective gear against impactsand their shocks, shock absorbers, e.g., packages or containers, as wellas for damping shocks in daily application, such as shoes, when thetransparency of the liquid state is beneficial as armor for windshieldsand electronic screens, optical actuators, civil engineering andbuildings, infrastructure and protection/mitigation against shocks bothby natural elements (such as earthquakes) and human-caused (such asexplosions—accidental or rocket/missile hits, and repetitive/expectedsuch as vibrations from moving vehicles or nearby drilling),temperature-controlled phase-change material such as for insulation fromheat (attenuates heating or cooling of the structure by absorbing orreleasing heat from the outside walls or roof), devices for computing(where the bit's 0 or 1 value may be determined by the material'sphase), tissue mimicking components or stand-alone materials (due to theability to fine-tune the stress flow properties and texture of thematerials, enable beneficial use in embodiments where control of thesetraits is needed, such as tissue mimicking for example, liver, musclesetc.), sports, agriculture, veterinary, industrial, transportation,astronomy, dental, medical devices and maritime, shock absorbers, shockattenuator, and energy mitigators.

In some embodiments the article may be used for personnel, instrument orcomponent, vehicular, and structural armor, solely or combined withother armor elements.

In some embodiments the article is in the form of a portioned (such ashoneycomb) sheet. In some embodiments the article is in the form of aninner layer of a multi-component armor, and may include rigid components(such as ceramics) or as a contained individual unit (such as in asealed “sleeve” for the elbow).

In some embodiments the article is used in a personal employment e.g.,joints (e.g., elbows, knees), such as in inner casings for helmets toprotect against concussions and brain lesions, and/or for repetitivesmaller amplitude shocks such as provided by shoe soles.

In some embodiments the article is used in civil engineering andbuildings, for infrastructure and protection/mitigation against shocksboth by natural elements (such as earthquakes) and human-caused (such asexplosions—accidental or rocket/missile hits, and repetitive/expectedsuch as vibrations from moving vehicles or nearby drilling.

In some embodiments the article may be implemented for military,security, sports, agriculture, veterinary, industrial, transportation,astronomy, dental, medicine, or maritime.

In some embodiments, the article may be implemented in designatedinstruments or in instruments and structures where control of acousticwaves is beneficiary.

In some embodiments, the article is implemented in acoustic insulationof devices.

In some embodiments, the article is an optical actuator.

In some embodiments, the transparency of the liquid state of thedisclosed composite is beneficiary for e.g., medical devices, armor forwindshields and electronic screens, etc.

In some embodiments, the disclosed temperature-controlled phase-changematerial is utilized. Such materials may be used in a variety ofapplications, e.g. structure insulation from heat (e.g., attenuatesheating or cooling of the structure by absorbing or releasing heat fromthe outside walls or roof) to computing (where the bit's 0 or 1 value isdetermined by the material's phase).

In some embodiments, the disclosed article is employed as tissuemimicking component, or stand-alone materials. The ability to fine-tunethe stress flow properties and texture of the disclosed articlematerials allow to enable beneficial use in embodiments where control ofsuch traits is needed, such as tissue mimicking (liver, muscles etc.).

Since, in some embodiments, the disclosed articles are expected to beresistant to wear at relatively high temperatures (e.g., 80-100° C.)they may serve as components in armors (e.g., helmets), protectiveshield, gels in vehicles, gels in systems with heating due tofriction—brakes, pistons, designable template (and spacer) for tubing,soft or flexible elements (for example: a flexible tube placed in asecond outer tube) which is filled with e.g., methyl cellulose solutionor with the disclosed composite in any embodiment thereof.

In exemplary embodiments, the tube may be bent and shaped into thedesired form, and then heated, thereby stiffening or rigidifying thetube.

Further exemplary articles are selected from shrink film wrap. In someembodiments, the disclosed article comprises mattresses, e.g., to reducevibrational shocks to the person deposited on the mattress.

In some embodiments, the disclosed article is used for the medicalpurpose of fixating a limb or other organs, such as a cast or scaffold.

In some embodiments, the disclosed articles can be employed by, withoutbeing limited to, personnel, instrument or component, vehicular, andstructural armor, solely or combined with other armor elements. In someembodiments, the personnel protection includes, but is not limited to:joints (e.g., elbows, knees) where the flexibility of the liquid stateis an advantage, sensitive organs such as in inner casings for helmetsto protect against concussions and brain lesions.

In one embodiment, the article is a portioned (such as honeycomb) sheetof the composite (see FIG. 30). In some embodiments, the disclosedarticle can be the inner layer of a multi-component armor or as acontained individual unit (such as in a sealed “sleeve” for the elbow,FIG. 31).

Further exemplary articles are selected from acoustic and shock-waveprotection devices e.g., a shock absorbers or acoustic insulators.

As exemplified in the Examples section below the liquid-state of thedisclosed composites show considerably higher attenuation of acousticwaves than water and lead. In additional exemplary embodiments, thearticles are selective acoustics component/adjustable hearing-rangesound and ultrasound coupling. Since the attenuation of ultra waves maybe temperature dependent, a component bearing the inverse-freezingmaterial (e.g., cellulose or methyl cellulose hydrogel) or the disclosedcomposite may be placed so that at a certain set temperature the wavespass through, and at another the waves are attenuated. This may allowcontrol of ultrasound amplitude past the component without requiringmechanical manipulation (such as physically removing barriers orchanging the angle of shutters), with simple heating bodies.

In some embodiments, the compositions, composites or articles disclosedherein may be used in various fields, including but not limited toprotection or improved performance of personal protection devices andaccessories, vehicles, instruments and their components, buildings orinfrastructures, vehicles, and robotics.

In some embodiments, the compositions, composites or articles disclosedherein may be used in various fields, including but not limited tosecurity, military, sports and leisure activities, civil engineering,maritime, medicine, veterinary medicine, agriculture, electronics,aeronautics and aerospace, industrial manufacturing, and transportation.

In some embodiments, the compositions, composites or articles disclosedherein may be used in various fields, including but not limited to useagainst harmful effects due to either human-sourced causes (such asballistic projectiles, explosions of warheads or explosive devices,drilling, vibrations caused by nearby active transportation) ornaturally-sourced causes (such as wildfires, earthquakes, volcaniceruptions).

In some embodiments, the compositions, composites or articles disclosedherein may be at least partially transparent (depending on theircomposition) such as for use as a protective layer for windshields invehicles or for display screens.

In some embodiments, the compositions, composites or articles disclosedherein may be used in various fields, including but not limited toengines (e.g., insulation of engine components such as pistons and/ormitigating heat due to friction).

In some embodiments, the compositions, composites or articles disclosedherein may be used in flexible tubing, as an external encaser of theflexible tube.

In some embodiments, the compositions, composites or articles disclosedherein may be used in shrink-wraps of various components of instruments,instruments, or goods.

In some embodiments, there provided a use of inverse-freezing materialor of composite comprising thereof as an element of one or more from: aprotective layer armor, a protective gear, a protective equipment, aprotective clothing, structural component for mitigation of shocks. Insome embodiments, the materials or the composite are coupled to anotherlayer of armor.

In some embodiments, the protective layer, or armor, is characterized byone or multiple layers comprising the inverse-freezing material or thecomposite, and further hard material, such as, without being limitedthereto, metals, ceramic material, inorganic oxide, Kevlar, ultra-highmolecular weight polyethylene.

In some embodiments, the layer(s) is in the form of either plate-like,flexible sheet-like, intermixed as a multi-component bulk (such asparticles of the hard material incorporated within the inverse-freezingmaterial or composite). In some embodiments, the thickness of each layercan be varied, between micrometers to several centimeters.

In some embodiments, the article comprises a first layer and an secondlayer, wherein: (i) the first layer and the second layer are heldtogether, (ii) the second layer (e.g., outer layer) comprises a hardmaterial and wherein (iii) the first (or inner) layer comprises theinverse freezing material or the composite, as disclosed herein. In someembodiments, the article is in the form of multiple layers (e.g., firstand second layers as described herein). In some embodiments, theinterior layer has a thickness of 1 micrometer to 3 cm.

In some embodiments, there is provided a shock-reducing mattresscontaining the disclosed inverse-freezing material or composite, e.g.,for reducing shocks passing to user lying thereupon.

General:

As used herein the term “about” refers to ±10%.

The terms “comprises”, “comprising”, “includes”, “including”, “having”and their conjugates mean “including but not limited to”.

The term “consisting of” means “including and limited to”.

The term “consisting essentially of” means that the composition, methodor structure may include additional ingredients, steps and/or parts, butonly if the additional ingredients, steps and/or parts do not materiallyalter the basic and novel characteristics of the claimed composition,method or structure.

The word “exemplary” is used herein to mean “serving as an example,instance or illustration”. Any embodiment described as “exemplary” isnot necessarily to be construed as preferred or advantageous over otherembodiments and/or to exclude the incorporation of features from otherembodiments.

The word “optionally” is used herein to mean “is provided in someembodiments and not provided in other embodiments”. Any particularembodiment of the invention may include a plurality of “optional”features unless such features conflict.

As used herein, the singular form “a”, “an” and “the” include pluralreferences unless the context clearly dictates otherwise. For example,the term “a compound” or “at least one compound” may include a pluralityof compounds, including mixtures thereof.

Throughout this application, various embodiments of this invention maybe presented in a range format. It should be understood that thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of theinvention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible subranges as well asindividual numerical values within that range. For example, descriptionof a range such as from 1 to 6 should be considered to have specificallydisclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numberswithin that range, for example, 1, 2, 3, 4, 5, and 6. This appliesregardless of the breadth of the range.

Whenever a numerical range is indicated herein, it is meant to includeany cited numeral (fractional or integral) within the indicated range.The phrases “ranging/ranges between” a first indicate number and asecond indicate number and “ranging/ranges from” a first indicate number“to” a second indicate number are used herein interchangeably and aremeant to include the first and second indicated numbers and all thefractional and integral numerals therebetween.

As used herein the term “method” refers to manners, means, techniquesand procedures for accomplishing a given task including, but not limitedto, those manners, means, techniques and procedures either known to, orreadily developed from known manners, means, techniques and proceduresby practitioners of the chemical, and mechanical arts.

It is appreciated that certain features of the invention, which are, forclarity, described in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures of the invention, which are, for brevity, described in thecontext of a single embodiment, may also be provided separately or inany suitable subcombination or as suitable in any other describedembodiment of the invention. Certain features described in the contextof various embodiments are not to be considered essential features ofthose embodiments, unless the embodiment is inoperative without thoseelements.

Various embodiments and aspects of the present invention as delineatedhereinabove and as claimed in the claims section below find experimentalsupport in the following examples.

EXAMPLES

Reference is now made to the following examples which, together with theabove descriptions, illustrate the invention in a non-limiting fashion.

Materials

Methyl cellulose type A15C Methocel, (A15C, Sigma Aldrich®) and methylcellulose (MC) SGA7CFood Grade (A7C, generously provided by DOW®Chemical Company) were used as received without further purification.Manufacturer reported values for percentage of methylation and viscosityof a 2% solution in water at 20° C. are: 27.5-31.5% (*D.S. 1.64-1.92)and 1200-1800 cP for A15C, and 29.5-31.5% (*D.S. 1.78-1.92) and 525-980cP for A7C. Water was purified by a Millipore Milli-Q instrumentreaching resistance of 18 MΩ.

Since the T_(g) can vary significantly with the heating rate, gelationtemperatures for the MC-based hydrogels in the heating rates used inthis work, 10° C./min, were measured by cloud-point (90% opticaltransference reduction, red-light LED in pulse mode (200 mA) set at 10cm from a det10A SI-biased photodiode detector (Thorlabs) with an addedamplification of ×50, with a thermocouple inserted into the hydrogelinto a sealed vial), these temperatures are detailed in Table 1 showingT_(g) at a heating rate of 10° C./min for the MC-based hydrogels in thisstudy, variance up to ±2° C.

TABLE 1 Concentration/ MC type A7C A15C gr/l ° C. ° C. 56 42 57 44 46 6128 50 64

Preparation of Four Exemplary Compositions (a Non-CompositeInverse-Freezing Material and Three Different Inverse-FreezingComposites)

A7C Methyl Cellulose Hydrogel

5 mL of purified water (obtained by using a Millipore Milli-Qinstrument) were heated in a capped vial with a magnetic stirring bar to70-80° C. 0.28 g methyl cellulose powder, SG-A7C-FG methocel (DOWChemical Company) was then added to the solution. The suspension wasmixed vigorously using a spatula, then the vial was recapped and placedin a water bath at 70-80° C. for at least 10 minutes while stirring. Thestirring bar was then removed and the capped vial was placed in an icebath for 60 minutes. The solution was then stored for at least 12 hoursin 1-4° C. before measurements.

A7C Methyl Cellulose Hydrogel with Polyvinyl Alcohol (PVA)

5 mL of purified water (obtained by using a Millipore Milli-Qinstrument) were heated in a capped vial with a magnetic stirring bar to70-80° C. 0.1 g polyvinyl alcohol (PVA), 99% hydrolyzed, Mw (average)146,000-186,000 g/mol (Sigma-Aldrich) was added to the heated water andstirred for 35 minutes, until no PVA particles were visible to the eye.Then, 0.28 g methyl cellulose powder, SG-A7C-FG methocel (DOW ChemicalCompany) was then added to the solution. The suspension was mixedvigorously using a spatula, then the vial was recapped and placed in awater bath at 70-80° C. for at least 10 minutes while stirring. Thestirring bar was then removed and the capped vial was placed in an icebath for 60 minutes. The solution was then stored for at least 12 hoursin 1-4° C. before measurements.

A7C Methyl Cellulose Hydrogel with Nano Boron Carbides

15 mg of nano boron carbide plate-shaped particles, with an averagediameter of 55 nm (American Elements) were weighed and inserted into aglass vial. 5 mL of purified water (obtained by using a MilliporeMilli-Q instrument) were added the vial, and then the dispersion wassonicated for 5 minutes. The solution was then heated to 70-80° C. in acapped vial equipped with a magnetic stirring bar. 0.28 g methylcellulose powder, SG-A7C-FG methocel (DOW Chemical Company) was thenadded to the solution. The suspension was mixed vigorously using aspatula, then the vial was recapped and placed in a water bath at 70-80°C. for at least 10 minutes while stirring. The stirring bar was thenremoved and the capped vial was placed in an ice bath for 60 minutes.The solution was then stored for at least 12 hours in 1-4° C. beforemeasurements.

A7C Methyl Cellulose Hydrogel with Cornflour (STIFF)

9 g of corn flour (starch from corn, Sigma-Aldrich) was inserted into aglass vial. 8 mL of purified water (obtained by using a MilliporeMilli-Q instrument) were slowly added, while thoroughly mixing thesuspension.

A shear thickening fluid forms. This fluid was then warmed to 60° C.,and then 0.4 g of methyl cellulose powder, SG-A7C-FG methocel (DOWChemical Company) was then added to the fluid, while slowly stirring.The vial was kept under heating in a water bath at 60-70° C. for atleast 10 minutes while slowly stirring, and then after the stirring barwas removed the capped vial was placed in an ice bath for 60 minutes. Itwas then stored for at least 12 hours in 1-4° C. before measurements.

Example 1 Ultrasonic Characterization

Experimental Methods

The longitudinal (V_(L)) and shear (V_(T)) wave speeds of the MC A7Cwere measured at 14° C. and 80° C., respectively. Since the velocitymeasurement itself, has inherent statistical scatter, a large number ofmeasurements (over 40 for V_(L) and above 10 for V_(T)) were performed.The ultrasonic experimental setup used for group velocity measurements,consists of a high voltage ultrasonic pulser (Olympus 5058PR) and twoultrasonic piezo-electric probes and two ultrasonic piezo-electricprobes, one for exciting and receiving longitudinal waves at a nominalfrequency of 1 MHz (SIUI-1M-24), and one for exciting and receivingshear stress waves at nominal frequency of 5 MHz (Olympus V152-RB). Themeasured ultrasonic signals were recorded using an oscilloscope (AgilentDSO-X 2004A, 2 Gsa/sec).

The ultrasonic measurements of the gels were performed using thepulse-echo technique. The liquid gel was cast into a cylindrical holderof Poly(methyl methacrylate)(PMMA), D=40 mm with a thin (0.2 mm) plasticslide as under plate, which was practically transparent to theultrasonic pulse and returning signals.

The raw data from each measurement includes at least four repetitivepulse echoes which were converted into rectified mode using Hilberttransform. A homemade Matlab code detects the location of the maximumamplitude of each pulse echo and calculates the group velocity(longitudinal/shear) using the following equation (1):

$\begin{matrix}{V_{g} = \frac{2X}{t}} & (1)\end{matrix}$

where X is the sample height and t is the time between two consecutivepeaks.

For the MC gel state, the Young's modulus (E) and Poisson's ratio (ν)can be calculated from the measured shear and longitudinal wavevelocities according to eqn. (2).

$\begin{matrix}{{E = \frac{V_{L}^{2}{\rho\left( {1 + \nu} \right)}\left( {1 - {2\nu}} \right)}{1 - \nu}}{v = \frac{1 - {2\left( {V_{T} - V_{L}} \right)^{2}}}{2 - {2\left( {V_{T} - V_{L}} \right)^{2}}}}} & (2)\end{matrix}$

where V_(L) and V_(T) are the longitudinal and the shear wave velocityrespectively and ρ is the material's density. For the liquid MC thecompressibility coefficient (β=dV/dP) can be calculated according toeqn. (3).

β=V _(L) ²ρ  (3)

-   -   where dV is the change in volume and dP is the change in        pressure.

The longitudinal (V_(L)) and shear (V_(T)) wave speeds of the MC A7Cwere measured at 14° C. and 80° C. respectively. Since the velocitymeasurement itself, has inherent statistical scatter, a large number ofmeasurements (over 40 for V_(L) and above 10 for V_(T)) were performed.

Results

The results are shown in FIGS. 1A-B and summarized in Table 2.

TABLE 2 Longitudinal Shear wave wave Young's velocity velocity modulus EPoisson's (m/s) (m/s) (GPa) ratio v Gel 80° C. 1699 ± 10  1010 ± 5 2.45± 2.91*10⁻⁵ 0.227 ± 0.005 Longitudinal Shear wave wave Compressibilityvelocity velocity coefficient (m/s) (m/s) β(1/GPa) Liquid 14° C. 1607 ±7   — 0.386 ± 0.003

Example 2 Compression Experiments for Methyl Cellulose Gels

Experimental Methods

Static Compression:

Uniaxial quasi-static compression experiments were conducted using ascrew-driven testing machine (Instron 4483), under displacement control,with a prescribed crosshead velocity of 3.6 mm/min. MC gels were testedinside a temperature controlled chamber, at a temperature of 80°±3° C.For high resolution force measurements, a 500N load-cell was installedon the machine. During the experiments the force (F) and thedisplacement (ΔL), were recorded at 8 Hz frequency.

In order to minimize frictional effects and thus avoid barreling of thesample (see FIG. 2), two custom glass plate adapters were installed onthe conventional compression gigs. Moreover, before each test, the glassplates were wetted with a few drops of water to reduce friction,achieving the sought-after effect.

Samples were cast into sealed glass vials with an internal diameter of18 mm. They were then heated in the temperature control temperature (setat 80° C.) for 4 minutes, to ensure a homogenous gel. The gel was thencarefully extracted out of the vial and sliced to yield a cylindricalsample with nominal diameter and height of D₀=18 mm, L₀=8 mmrespectively. Pictures of a sample before and after compression arepresented in FIG. 2.

The measured load-displacement curves were reduced into engineeringstress-strain curves, where the engineering stress (σ_(eng)) wascalculated as the applied load divided by the original cross sectionarea (A₀).

$\begin{matrix}{\sigma_{eng} = \frac{F}{A_{0}}} & (4)\end{matrix}$

Hence, the engineering strain (ε_(eng)) was calculated as

$\begin{matrix}{ɛ_{eng} = \frac{\Delta L}{L_{0}}} & (5)\end{matrix}$

where L₀ is the original specimen height and ΔL is the measuredextension.

Repeatability and homogeneity: The repeatability experiments wereconducted on specimens with MC concentration of 56 gr/l at temperatureof 80° C. The flow stress measurements of A7C and MVM were repeated 3 to10 times. Each curve was collected from separately-prepared batches, andnot averaged out.

Furthermore, with the aim of characterizing the spatial homogeneity ofthe sample, different portions of the same sample were testedseparately. Since the gel sample may be stored for a few days before theexperiment and is not stirred before measurement, it was important torule out sedimentation of the polymer. Such a process might cause astrain gradient in the specimen, so that the upper part might be muchweaker than the lower part. For this purpose, four A7C specimens werestored for 4 days at 4° C., heated to 80° C. and split into half. Eachof these portions were tested separately.

Characterization of the semi-solid gel: A7C and MVM samples at threedifferent concentrations, including 28, 44 and 56 gr/l werecharacterized at 80° C. In addition, the mechanical response of MC atthe gelation temperature (65° C.) was compared to semi-solidtemperatures of 80° C. and 100° C. with a fixed gel concentration (44 or56 gr/1). The strain rate sensitivity of semi-solid A7C was examinedwithin a range of nominal strain-rates between 7.5*10⁻³-4*10⁻¹ l/sec andwith concentration of 56 gr/l at 80° C.

Dynamic Compression:

The dynamic compression experiments were performed using a conventional12.7 mm diameter Kolsky apparatus as illustrated in FIG. 3A, made of7075-T6 aluminum-alloy bars, which were loaded at the far end of theincident bar with a projectile made of the same material.

Once the striker hits the incident bar, a compression stress wavepropagates along the incident bar until it reaches its end. At thatpoint, the stress wave reaches the interface between the incident barand the specimen. Here, part of the incident stress wave propagatesthrough the specimen into the transmitted bar, while another partreflected back in the incident bar. The incident, reflected andtransmitted stress waves, ε_(inc), ε_(ref), ε_(tra) respectively, aremeasured by strain gauges (S.G) and recorded using a Nicolet 440 digitaloscilloscope. The displacements and the forces acting on each side ofthe specimen can usually be obtained from 1D wave propagation analysis.The applied forces on each side of the specimen are calculated based onthe measured strains, and can thus be checked for dynamic forceequilibrium.

F ₁ =AE(ε_(r)+ε_(i))

F ₂ =AE(ε_(t))  (6)

1D wave analysis based on S.G measurements usually fits when the testedmaterial has acoustic impedance close to the acoustic impedance of theHopkinson bars. For low amplitude forces measurements, a standard 201HTFlexi-force™ (FF) force sensors were placed on the edges of theHopkinson's bar as illustrated in FIG. 3B, so that the interfacialforces are measured directly and not through signal analysis.

-   -   A pulse shaper, consisting of soft paper mixed with a carefully        measured amount of molybdenum disulfide grease, was inserted        between the striker and the incident bar. The pulse shaper is        used to increase the rise time of the loading pulse thereby        improving the specimen equilibrium due to lowered accelerations.        Due to the use of pulse-shapers, the strain rate is not constant        throughout the tests as it increases with strain to reach a peak        value. The reported strain rates are the peak values.    -   In order to ensure constant environmental temperature and        humidity to 70° C. and 100% respectively, a sealed heating        chamber was designed and built.    -   To validate the FF sensors' response, the volt to force relation        was measured at the beginning and at the end of each        experimental set by performing three shots without specimen        between the Kolsky bars, as shown in FIG. 4A. The experimental        force history was compared recorded signal on the two FF        sensors, as shown in FIG. 4B.

The dynamic force equilibrium was measured directly with the FF gauges,by comparing the forces on both sides of the samples at a strain rate of˜1500 l/secin the range of 1-12N, using the split Hopkinson pressure bar(Kolsky apparatus). The dynamic compression true stress and true strainof A7C were calculated from split Hopkinson experiments, where themaximum strain rates were in the range of 1000-1600 l/sec at 70° C.

Comparison Between Static and Dynamic Compression

The dynamic and quasi-static flow curves were compared in order toexamine the strain rate sensitivity of A7C methyl cellulose hydrogel(abbreviated hereon as MC for methyl cellulose and A7C for the SG-A7C-FGmethocel hydrogel) in a qualitative manner. Unless otherwise mentioned,MVM is an abbreviation of medium viscosity methyl cellulose, of the A15Ctype, hydrogel.

Results

Static Compression:

Repeatability and homogeneity: FIG. 5 presents high degree ofrepeatability in the quasi static measurements of the MC samples. ForA7C samples, up to a strain of 0.15, there is very little hardening, butfrom that point on, the gels stiffen (hardens) rapidly. The samebehavior was observed for MVM from stretch of a 0.2. FIG. 6 presents thesample homogeneity and stability, as no difference was observed in thestress-strain curves of the various tested specimens. Moreover, sampleswhich were stored for 14 days at 4° C., exhibited similar flow stress tospecimens with minimal storage time (12 hours).

Characterization of the semi-solid gel: FIG. 7 shows the strengtheningof MC gel with increasing polymer concentration. For instance, at astrain of 0.5 the A7C sample with 28 gr/l possesses a flow stress of ˜33KPa; by doubling the concentration of MC in the sample, the flow stressat the same strain is increased by 10 fold to ˜328 KPa. Similarly, butto a lesser extent, MVM with a concentration of 28 gr/l, at a strain of0.5, possess a flow stress of ˜12 KPa, while MVM with a concentration of56 gr/l, possesses a flow stress of ˜60 KPa. With higher content ofpolymer chains, including loci of interactions between them, moreassociation sites are available and a denser 3D fibrillar network canform, over larger volumes of media. Such networks confer to the gel anincreased ability to resist strain and therefore a higher flow stress.

FIG. 8 shows the uniqueness of the thermo-reversible gelationphenomenon: the gels stiffen as the temperature increases.Interestingly, even at 65° C., that is just a few degrees above thegelation temperature of MVM (and about 10° C. above the gelationtemperature of A7C), both gels exhibit reproducible, solid-likemechanical behavior. For example, at a strain of 0.5 the A7C sampletested at 65° C. exhibits a flow stress of ˜92 KPa; by increasing thetemperature to 100° C., the flow stress reaches to ˜247 KPa which isabout 2.5 folds enhancement. MVM exhibits an even larger hardening (6folds). For a strain of 0.5, the flow stress of MVM shifts from ˜24 KPaat 65° C. to ˜150 KPa at 100° C. The same trend was observed in FIG. 9,showing that this phenomenon is not unique to a single concentration ofthe MC polymer in the hydrogel.

According to FIG. 10, there is no evidence for strain rate sensitivityin the investigated range of strain rates (quasi-static regime). Theseresults were rather surprising, since many soft gels tend to exhibitstrain rate sensitivity.

Temperature and Polymer Concentration

A7C and A15C-based hydrogel samples at three different concentrations,28, 44 and 56 gr/l respectively, were prepared and measured. Typicalstress-strain curves of these samples with different concentration at atemperature of 80° C., are shown in FIG. 11. FIG. 11 shows that thestrength of the MC-based gel increases with increasing polymerconcentration. For instance, at a strain of 0.5 the A7C sample with 28gr/l possesses a flow stress of ˜33 KPa; by doubling the concentrationof MC in the sample, the flow stress at the same strain is increased bytenfold to ˜328 KPa. Similarly, but to a lesser extent, A15C-basedhydrogel with a concentration of 28 gr/l, at a strain of 0.5, possess aflow stress of ˜12 KPa, while A15C-based hydrogel with a concentrationof 56 gr/l, possesses a flow stress of ˜60 KPa. As can be seen, for allconcentrations examined A7C-based hydrogels consistently show higherflow-stress than A15C-based hydrogels. This could be due both to theaverage larger values of DS for the A7C-type.

With higher content of polymer chains, including loci of interactionsbetween them, more association sites are available and a denser 3Dfibrillar network can form, over larger volumes of media. Such networksconfer to the gel an increased ability to resist strain and therefore ahigher flow stress.

Characterizing the influence of the temperature on the mechanicalproperties of our gels is essential since these properties changeconsiderably on crossing the gelation temperature. Therefore, themechanical response of a fixed selected gel concentration of 56 gr/l wasinitially measured at the lowest temperature, that is still above theT_(g) of the lowest-T_(g) sample (65° C.) as a reference. Then,additional samples were stabilized at temperatures of 80° C. 100° C.,and then tested. Typical flow curves of A7C and A15C-based hydrogelsamples are shown in FIG. 12.

FIG. 12 shows the uniqueness of the thermoreversible gelationphenomenon: the gels stiffen as the temperature increases.Interestingly, even at 65° C., both gels exhibit reproducible,solid-like mechanical behavior. For example, at a strain of 0.5 theA7C-based hydrogel sample tested at 65° C. exhibits a flow stress of ˜92KPa; by increasing the temperature to 100° C., the stress reaches avalue of ˜247 KPa which is about 2.5 times larger. A15C-based hydrogelexhibits an even larger hardening (six folds). For a strain of 0.5 theflow stress of A15C-based hydrogel shifts from ˜24 KPa at 65° C. to ˜150KPa at 100° C.

In order to verify that this stiffening with increased temperature isnot unique only to the gel with the specific concentration describedabove, MC gels with another polymer concentration of 44 gr/l were alsoprepared and tested. Flow stress curves of A7C-based hydrogel at thisconcentration compared to the 56 gr/l samples are shown in FIG. 13 as afunction of the temperature.

The results in FIG. 13 imply that temperature-caused increase of gelflow stress occurs over a range of concentration of MC polymer in thegel.

this is the first demonstration of MC gel-state mechanical stiffening asa function of strain, by heating beyond the gelation point, asdetermined by straightforward monotonic compression tests, thatcomplements the previous report.

Rheological experiments have shown that G′, as a function of angularfrequency up to values of 100 (rad/sec), reaches a plateau at around 65°C.-70° C. in the second stage of heat-induced gelation, corresponding tothe formation of a strong gel. A more recent investigation reveals thatthe gels' plateau storage modulus, as a function of applied rheologicalstress, increases (from certain stresses upwards) with temperature. Thisremarkable behavior occurs only above T_(g), and is attributed to thegel's fibrillar structure, distinct from other soft gels comprised ofentangled flexible polymers. These novel findings therefore provideadditional evidence that the gel's response to heating is not similar tothose of the majority of other solids, either crystalline or classicamorphous (such as glass).

Heat applied to most known solids causes increased vibration of theircomponents and weakening of their bonds (whether intermolecular inmolecular solids or covalent/ionic in atomic solids), leading todecreased flow stress. However, MC hydrogels exhibit just the oppositebehavior (at least in the examined temperature range). Since care wastaken to prevent loss of water, increasing polymer concentration throughsolvent loss from the gel is an unlikely explanation of the results.While the underlying cause of this phenomenon requires further study, itis proposed, without being bound by a particular theory, that uponheating, association between more polymer chains continues to occur,shedding of structured solvent, formation of more fibrils and theirgrowth, increasing network density and in turn leading to higherstiffness.

Dynamic Compression:

The force histories shown in FIG. 14 indicate satisfactory dynamic forceequilibrium. Therefore, the strain can be reliably calculated using thereflected signal Cr. In a few cases where a satisfactory state ofdynamic equilibrium was not achieved (due to the gel's acousticimpedance and high attenuation), the stress strain curves were comparedto experiments showing satisfactory dynamic force equilibrium (in orderto assess a good fit). FIG. 15 shows the representative true stress truestrain curves and the span (scatter) of failure strains for testscarried out at relatively similar strain rates.

Comparison Between Static and Dynamic Compression

FIG. 16 demonstrates the flow stress increase of A7C gel by 600% at astrain of 4.5% up to an increase of 1800% at a strain of 15% by dynamiccompression compared to the quasi-static loading.

Example 3 The Additives' Effect on Methyl Cellulose Gels Characterizedby Quasi-Static Compression Experiments

Materials and Methods:

Quasi-static experiments were conducted on 4.4% of MVMorA7C by weightwith and without polyvinyl alcohol (PVA), a polymer additive, in gr per5 ml of solution. The mechanical properties of MVM were also evaluatedby increased concentrations of PVA polymer.

In addition, several types of particles at different concentrations wereexamined as additives to A7C by quasi-static and dynamic compressionexperiments including silica particles with diameter of 0.063-0.200 mm,fumed silica (aerosol 200 and 300), aluminum nanoparticles with diameterof 70 and 100-200 nm, micro-sized rhombohedral boron carbides (B₄C) withdiameter of ˜0.7 μm—abbreviated henceforth as “fine boron carbides”,“fine BC” or “FBC” and B₄C nanoparticles with diameter of 45-55 nm(99+%, hexagonal, from US Research Nanomaterials, Inc.)—abbreviatedhenceforth as “nBC” or “nano BC”.

A combination of 50% of corn flour with 5.3% A7Cby weight was alsotested as additive. Corn flour is a starch and as hear thickening fluid(STF) that characterized by its ability to increase viscosity(abbreviated henceforth as STIFF).

All experiments were conducted at 70-80° C.

Results:

Interestingly, although according to FIG. 17, PVA increased flow stressfor MVM, it decreased the flow-stress of A7C, as shown in FIG. 18.

Example 4 Nano Boron Carbide Particles as Additives in the Composite,and their Effect on Methyl Cellulose Gels Characterized by Quasi-Staticand Dynamic Compression Experiments

FIGS. 19-20 show that B₄C particles (nano or micro sized) addition toA7C had the largest increase of the flow stress. Among the specificconcentrations examined of micro-sized B₄C, a weight of 0.3% showed thehighest rigidification, as demonstrated in FIG. 21.

FIG. 20B presents characteristic stress-strain curves for quasi-static(7.5·10⁻³ sec⁻¹) compression of pristine MCH (5.6% wt. MC in water,black curve) and boron carbide-methyl cellulose BC-MC composite gelswith various sized BC particles (5.6% wt. MC, 0.3% wt. BC particles, inwater), at 80° C. While composites based on BC particles with a widedistribution of sizes, from ˜1 μm. to ˜0.1 μm, failed to improve theflow stress compared to non-composited MCH, narrowing the particle sizedistribution shows noticeable improvement. Since nano sized BC particleswith an average size of 50 nm, showed better improvement than larger,sub-micronic particles, composites based on these particles (nBC-MC)were focused upon for further study.

Moreover, FIGS. 20 and 22 demonstrate that effect of B₄C nanoparticles.Therefore, the dynamic compression of a composite of A7C and 0.3% weightB₄C nanoparticles was examined.

Comparison of the stress-strain curves shows that under dynamiccompression conditions, nBC-MC gels display a very sharp rise in flowstress, starting from an early strain of ˜5%. The strain hardening slope(dσ/dε) is about 38.7 MPa, and the peak stress is achieved at ˜7%strain, with a stress of ˜500 kPa. In contrast, pristine MCH showssignificantly weaker dependence on strain, with a strain hardening slopeof about 1.6 MPa. It reaches a peak stress at a strain of ˜15% with astress of ˜200 kPa. It is noted that the increased dynamic strength isaccompanied by a significant reduction in ductility of the material.

FIG. 23A illustrates its increase flow-stress by 2400% at a strain of 1%and up to an increase of 44700% at a strain of 6%, in comparison to theA7C hydrogel alone, non-composite. Both solid states were examined at70° C., under a strain rate of 1500 l/sec.

FIG. 23B presents characteristic stress-strain curves for quasi-static(7.5·10⁻³ sec⁻¹) and dynamic (1,700 sec⁻¹) compression of pristine (5.6%wt. MC in water) and nBC-MC composite gel (5.6% wt. MC, 0.3% wt. nano-BCin water), at 80° C.

The extreme enhancement in mechanical properties due to the addition ofonly 0.3% wt. of nanoparticles is surprising. Noticeable effects onmechanical properties are normally achieved only at significantly higherparticle concentrations.

It surmised, without being bound by any particular theory, that if thenano-BC particles interact with critical sites in the gel structure,such as fibrillar nodes or intersection sites of different fibrils, theycould affect the macro-sized structure in a sufficiently significantmanner. From a supramolecular chemistry approach, such particle-polymerinteractions likely involve interactions between lone pair electrons ofoxygen atoms in the polymer with the empty orbitals of boron atoms onthe surface of BC particles. Evidence of such attractions within thecomposite was searched using cryo-TEM to study a dilute composite gel(1% wt. MC, 0.05% wt. nano-BC in water). This provided a directvisualization of particle-polymer interactions, see FIG. 23C-D.

Using the free fibrils within the gels as reference, the considerablydarker register of the outline of the nano-BC aggregate in the cryo-TEMimages signifies dense MC structures. This is even more conspicuous inlight of the use of phase plates in the imaging, which generatesbrighter outlines around distinctive features. Although the imagesprovide evidence of the MC interacting with the external surface of theaggregate, it is possible that the polymers are also present within it,between the nano-BC plates. Since MC is a polysaccharide with onlypartial methylation of its hydroxyl groups, even when it assumes foldedpolymer structures, as is currently thought to be the case in fibrils,it should have numerous sites capable of interacting with the nano-BCparticles.

Further support for this interaction is found in the control experimentsperformed to examine the stability of the BC-MC solutions. Samples ofthe composites were left in refrigeration (4-8° C.) for at least twoweeks. After heating the sample to beyond its gelation temperature (80°C.) in a vial, the resulting cylindrical gel was extracted and cutacross the equator. Each of the portions, upper and lower, were studiedunder quasi-static mechanical compression, and showed no difference inmechanical properties between the portions.

FIG. 24A shows that the stress-flow curve of a composite of A7C withcorn flour as additive (50% weight), for purpose of shear thickeningbehavior, was similar to the curve of A7C alone, in the quasi-staticregime (these rates are below the onset of shear thickening). Thiscomposite, despite the large weight percentage of the additive, stillhas the behavior of an inverse-freezing material (gelates upon heating).

Example 5 Improvement of Stf Shock Mitigation by Incorporation ofInverse-Freezing Materials

In additional exemplary procedures it was demonstrated that shearthickening fluids show very little attenuation of shocks (FIG. 24B) −2cm thick solution of 106 g cornstarch with 100 mL water shows 4%reduction of maximum amplitude of forces. However, their combinationwith even small percentages of IF-enabling components leads tosignificant shock attenuation.

In additional example, 129 g cornstarch mixed with 120 mL. 3% aq.methylcellulose solution leads to a shear-thickening inverse-freezingsolution. The shock attenuation of this composite fluid at a 2 cm.thickness is found to be 56% reduction of maximum amplitude of forces.The shock attenuation of this composite fluid is demonstrated in FIG.24C.

Example 6 Temperature-Dependent Attenuation Effect of Methyl Cellulose

Materials and Methods:

The inverse freezing material is liquid in room-temperature and becausesome of the applications are shock absorbers or armor components intheir ambient-temperature, liquid states, the following experiments wereconducted. The material was confined into a small metal chamber andthen, under confinement, was subjected to a mechanical impact using aone bar Hopkinson setup made of 7570-T6 Aluminum alloy, as shown inFIGS. 25A-C. The energy loss (attenuation, or damping) caused by theconfined liquid state was compared to water, after reduction of theexperimental system's inbuilt loss was taken into account in both cases.

Results:

FIG. 26 demonstrates that diluted MVM (3% weight) had an energy loss ofmore than 120% compared to water according to 84 measurements of 41specimens of MVM and 39 measurements of water (with system energydamping of 5% tested by 38 measurements), for impacts of 1000-2000Newton at the peak and speed of 4-6 m/sec. Despite the largedistribution of values for the sample, its improved energy damping isstatistically significant. It is further noted that the optimalperformance of the sample was when the energy loss values rise to over50% compared to water (less than 10%), thus these samples have a 500%increase in mechanical impact energy damping. This finding shows thateven at relatively low polymer concentrations in the hydrogel, theliquid state of this inverse-freezing material is capable of high energydispersal/absorption/mitigation of dynamic impacts, at ambienttemperatures (these measurements were performed at 20-25° C.

FIG. 27 illustrates the A7C ultrasonic wave velocity changes from 1607to 1699 m/sec when the temperature rises from 14° C. to 80° C. Suchtemperature-dependent behavior can be discerned when examining thereflection pattern of the signals travelling within a sample—clearchanges in reflectance to reflectance durations can be seen withtemperature variation, especially around the gelation temperature. Suchdependence is not discernable in ballistic gelatin, for example, underthe same conditions.

The temperature attenuation coefficient of liquid and solid A7C rangesbetween 0.4-0.55 Np/Cm at frequencies of 400 KHz to 1 MHz as shown inFIGS. 28-29. The attenuation of these frequencies is a challenging taskcurrently, and even the modern armors have lower attenuationcoefficients than this. For comparison, the attenuation coefficient ofwater at these frequencies is twenty times smaller than that of A7C.

Example 7 Shock Testing Systems and Shock Attenuation ofInverse-Freezing Materials

In exemplary procedures, the testing system included a Hopkinson Bardynamic system with strain gauges on the bar and a box whose front was ametal plate fixated perpendicularly to the impact bar which impacts itfrom the front. Behind the metal plate a rectangular chamber holdsvarying thicknesses of the inverse-freezing liquid, or water asreference. The width of the gap between the front plate and the backwall can be adjusted, thus enabling to study the response of differentthicknesses of the inverse-freezing fluid. Force sensors were installedto sandwich this liquid layer from its front (set on the backside of thefront metal plate)—providing a reading of the force signal entering thelayer due to impact on the front plate, and on its back (set on thefront of the hind wall)—providing a reading of the force signal thatpassed through the liquid. This latter simulates the force that wouldhit a wearer of an armor comprising a front, projectile-penetrationpreventive hard layer, and second, shock attenuating layer closer to thewearer's body. FIGS. 32A-B provide a visual description of the system.

FIG. 32A presents a general structure of the experiment system viewedfrom above, with some components specified. FIG. 32B general side viewof the system, more clearly showing the inverse-freezing materialfilling within its chamber (the yellow-brown conductors are those of theforce-sensors).

Results

Impact Forces and Impulses

In some experiments, the impactor driving pressure of 1.5 bar provided amaximum force amplitude of 10,000 Newton. In another, the impactordriving pressure of 4 bar provided a maximum force of 20,000 Newton.This provides impact impulses that are in the range of 40-75% of thoseof a 5.56 mm bullet fired from an M4 assault rifle impacting a target ata range of 50 m.

FIGS. 33A-B present force amplitude graphs measured for two differentimpactor driving pressures (specified at the upper left corner in eachgraph).

Attenuation of the Impact Forces Applied to the Layer

The inverse freezing materials were found to have immediate attenuationof the applied forces, in addition to the attenuation of propagatingstress loads (discussed in the following sections). For example, for amaximal force amplitude of 20,000N (see profile in the graph of FIG.33A) a 5% w/w aqueous methylcellulose solution mitigates the incomingforce of the impact 3.5 times better than water. Details are provided inFIG. 34 showing that even at small thicknesses, these materials provideattenuation for incoming impacts.

Attenuation Performance of a 5% w/w Methylcellulose Aqueous Solution

The performance of a 5% w/w methyl cellulose aqueous solution at roomtemperature (the inverse freezing material is thus in its liquid state)was compared to that of water, both at 2 cm. thickness.

Comparison of the force signals incoming into the material with thosepassing through the material show a 45% percent reduction of the maximumamplitude of the force, and a ˜40% reduction of the impulse. Incomparison, water alone shows 2.9% reduction of the maximum amplitude ofthe force, and a ˜3% reduction of the impulse. FIGS. 35A-B provide thecomparison data.

In additional exemplary procedures, 5% wt. aq. methylcellulose, theshock attenuation based on maximum forces' amplitude was measured beforeand after the medium, denoted as Fin as Fout (FIG. 36A). Attenuation of45% of maximum amplitude of forces passing through 2 cm of the materialwas found. This is in comparison to water (FIG. 36B) which showed (usingthe same setup and 2 cm thickness) attenuation of 3% of maximumamplitude of forces, and 5% wt. aq. ballistic gelatin (bloom 300) withthe same setup and 2 cm thickness which showed attenuation of 17% ofimpact forces (FIG. 36C).

In additional exemplary procedures, a composite comprising 1 cm thick 5%wt. aq. hydroxypropyl methylcellulose was tested for attenuation basedon Fin vs. Fout of impact (FIG. 36D). Attenuation of 20% of maximumamplitude of forces passing through the material was found.

In additional exemplary procedures, a composite of 1 cm thick 5% wt. aq.methylcellulose and 5% wt. poly(2-ethyl-2-oxazoline) was tested forshock attenuation based on Fin vs. Fout amplitudes (FIG. 36E).Attenuation of 8% of impact forces passing through the material wasfound.

In additional exemplary procedures, a composite of 1 cm thick 5% wt. aq.methylcellulose and 0.3% wt. nano Boron Carbides was tested forattenuation based on Fin vs. Fout of impact (FIG. 36F). Attenuation of33% of maximum amplitude of forces passing through the material isfound.

Additional exemplary procedures aimed at using inverse-freezingmaterials and composites as shock-absorbers/attenuators due to phasetransformations at the interface with impacted/impacting material, suchas a hard front plate or hard elements within the material.

It is noteworthy, without being bound by any particular mechanism, thatthis attenuation is a property of the inverse freezing material and isnot simply a matter of wave reflection due to acoustic impedancemismatch.

In exemplary procedures, incoming forces were applied on into 5% wt. aq.Methylcellulose. The attenuation was based on strain-gauge on impactingbar vs. Fin, when the 5% wt. aq. methylcellulose was coupled to analuminum front plate, with the methylcellulose as a second layer inarmor (FIG. 37A). Attenuation of 90% of maximum amplitude of forcesentering the inverse-freezing material was found. This is in comparisonto water (FIG. 37B-C; strain gauge forces, and performance of water vs.IF liquid, respectively). It was found that the inverse freezing liquidattenuated the maximum amplitude of incoming forces more than 3.5 timesbetter than water—incoming forces of 2000 N vs. 8000 N respectively, forthe same setup and forces of striker.

In additional exemplary procedures 2 cm thick sample of 5% wt. aq.methylcellulose attenuates shock the same as a 1 cm thick sample of 5%wt. aq., for the same shock, in the same experimental setup. Bothattenuate 35-45% of maximum amplitude of forces Therefore, it seems thatthe inverse-freezing material or the composite's attenuation of shocksis not thickness-dependent (FIG. 37D, compare to FIG. 36A to seesimilarity).

A spectral analysis providing data on the spectral attenuation showsthat the inverse freezing solution provides nearly full attenuation ofthe frequencies above 20 KHz. Near 0 KHz the attenuation is about 20%and grows in size with increasing frequency. FIGS. 38A-B provide visualdata.

Attenuation Performance of a 10% w/w Methylcellulose Aqueous Solution

The performance of a 10% w/w methyl cellulose aqueous solution at roomtemperature (the inverse freezing material is thus in its liquid state)was compared to that of water, both at 2 cm thickness.

Comparison of the force signals incoming into the material with thosepassing through the material show a 77% percent reduction of the maximumamplitude of the force, and a 69.5% reduction of the impulse. Incomparison, water alone shows 2.9% reduction of the maximum amplitude ofthe force, and a 3.4% reduction of the impulse. In exemplary procedures,2 cm thickness 10% wt. aq. Methylcellulose was used, and the shockattenuation based on Fin vs. Fout amplitudes before and after the mediumwas measured. Attenuation of 71% of maximum amplitude of forces passingthrough the material was found (FIG. 39).

A spectral analysis providing data on the frequencies of attenuationshows that the inverse freezing solution provides nearly fullattenuation for all impact frequencies. FIG. 40 provides the visualdata.

High-Speed Photography

Aiming to gain more in-depth understanding into how these materialsachieve such efficient attenuation, high-speed photography was appliedto follow the AMC solution as it responds to impact. A custom-made lowreflectivity chamber, equipped with a transparent window and an orificefor the insertion of the Hopkinson impacting bar, was filled with the5.6% wt. AMC solution. Control experiments were performed on water andon 5% wt. ballistic gelatin using the same cell and setup, see FIG. 41A.

Frames b-e of FIG. 41B depict time-lapse pictures of the AMC gelfollowing impact. Volume oscillations (pulsations) of air bubbles,trapped inside the gel, indicate the recurrent passage of stress-wavesacross the sample. An optically opaque front develops on the edge of thebar ˜50 microseconds after the impact, and grows to 3-5 mm depth withinthe following ˜300 microseconds. This front progresses at a velocity of˜50 m·s⁻¹, which is much slower than the stress waves, whose velocity isabout 1600 m·s⁻¹.

In order to rule out reasons for the impact-induced opacity other thangelation, two control experiments were carried out. An experiment withnear identical loading conditions was performed on pure water, as theycompose 94.4% wt. of the AMC system. A second control experiment wascarried out on 5% wt. ballistic gelatin, the most extensively studiedorganic aqueous gel material in impact experiments. However, in bothcontrol experiments only the formation of trapped oscillating airbubbles was observed, FIG. 41B frames f-l and frames j-m respectively.Cavitation as a possible cause for opaqueness is also excluded since theair bubbles, present throughout the samples clearly “pulsate” in size.This volume oscillation originates from reflections of the fastertravelling elastic stress-waves within the medium, and is incompatiblewith conditions required to form a cavitation-induced advancing front.

It is therefore proposed that the process occurring within the sample inthe area most proximal to the bar's leading edge, originates from therapid shock-induced gelation of the AMC following impact. The opacitywould therefore arise from structures of large enough size to scattervisible light, although these structures would not necessarily be ascomplex as those obtained by slow heating. This gelation may stem fromseveral sources, among which are the local heating and the largeincrease, ˜150 fold, of local pressures caused by the impact. The effectof high pressure on AMC gel formation has not yet been reported. Furthersupport for the proposed mechanism can be derived by straightforwardenergy considerations. The enthalpy of gelation of AMC solution is onthe order of 0.7 J·mL⁻¹. The energy delivered into the sample wascalculated based on the difference between impact and reflected elasticwaves, recorded using strain gauges on the impact bar. Calculations andmeasurements clearly indicate that the energy delivered to the sampleupon impact in all cases exceeds the energy required to induce gelationin the volume in which opacity is observed by a factor of at least 1.7,see Table 3, showing energy values provided by the impacting barcompared to those required for AMCs to undergo gelation, in four typicalexperiments.

TABLE 3 Energy Impact required energy, for Ratio of in gelation impactDepth of Volume volume in the energy Strain observed of of observed toExp. energy gel front formed observed volume gelation No. (Pa) (mm) gel(mL) gel (J) (J)* energy 1 1.23 · 10⁶ 3.0 0.38 0.47 0.27 1.7 2 1.31 ·10⁶ 4.4 0.56 0.87 0.39 2.2 3 2.57 · 10⁶ 4.4 0.56 1.43 0.39 3.7 4 2.82 ·10⁶ 4.3 0.54 1.53 0.38 4.0

-   -   The surface area of the bar is constant for all experiments,        12.7 mm. The depth of the observed gel front was measured from        the films. *Values are 0.7 J·mL⁻¹.

By applying statistical analysis on pixel brightness, the kinetics ofgelation may be unveiled, FIG. 42.

In a typical impacted AMC solution, a delay time of ˜100 microsecondsprecedes the formation of the opaque front, which presents a rise-timeof ˜200 microseconds. The obtained sigmoidal curves are similar to thosereported for gel formation by slow heating in rheological measurements,where the storage and loss moduli are plotted as a function ofincreasing temperature. When the impacting bar is in close proximity tothe rear wall of the chamber, the formation of gel can be observed inthis site as well, as the appearance of a second opaque front, see FIG.43. In contrast to the moving bar, the rear wall is a non-hindered sitefor observation, in which the conditions of heat and pressure for gelformation are also met. In such a setup, the delay time for observed gelformation shortens somewhat but the rise-times remain similar.

AMC was previously well-known to gelate in a thermally-induced process,but this complementary impact-induced gelation is presented here for thefirst time. This new mechanism can explain the energy uptake and largeshock-attenuation observed for impacted, room-temperature AMC. Becauseof their unique transition to solids upon heating, this behavior mayoccur also in other families of inverse-freezing materials. Thus, theherein disclosed findings unfold a new potential to harness thesematerials for shock mitigation or energy dissipation purposes, and forother applications requiring very rapid response of liquid materials.

Although the invention has been described in conjunction with specificembodiments thereof, it is evident that many alternatives, modificationsand variations will be apparent to those skilled in the art.Accordingly, it is intended to embrace all such alternatives,modifications and variations that fall within the spirit and broad scopeof the appended claims.

What is claimed is:
 1. An article having at least one energy mitigatingwall comprising a first metal layer in contact with an interior layer,and an additional metal layer in contact with said interior layer;wherein said interior layer comprises an inverse freezing material. 2.The article of claim 1, wherein said metal comprises aluminum.
 3. Thearticle of claim 1, wherein said interior layer is characterized by athickness of between 0.1 um and 10 cm.
 4. The article of claim 1,wherein said metal layer is characterized by a thickness of between 1and 100 mm.
 5. The article of claim 1, being in a form of a packagingarticle or a container.
 6. The article of claim 1, wherein said inversefreezing material is present within said interior layer at an amountsufficient to provide at least one of: (i) attenuation coefficient inthe range of 0.4-0.55 Np/Cm at frequencies of 400 KHz to 1 MHz; (ii) anincrease of flow stress of at least 10% at strains higher than 10%, uponincreasing the temperature from the gelation temperature (Tg) to 100°C.; (iii) an increase of flow stress by at least 200% in response to astrain above 4% applied to said article at a strain rate above 103l/sec, in comparison to a flow stress in response to said strain appliedto said article at a strain rate below 1 l/sec, at a temperature abovethe Tg of said inverse-freezing material; (iv) an increase of flowstress by at least 200% at a temperature ranging from the of saidinverse-freezing material to 100° C.
 7. The article of claim 1, whereinsaid inverse-freezing material comprises a polymer selected from thegroup consisting of: a cellulose derivative, amphiphilic polymer,Polysuccinimide, N-alkyl substituted acrylamide, Poly-4-methylpentene-1(P4MP1), Polyethyleneoxide-polypropyleneoxide-polyethyleneoxide(PEO-PPO-PEO), poly(2-ethyl-2-oxazoline, poly(ethylene oxide)-polylacticacid block copolymer, or any combination thereof.
 8. The article ofclaim 1, wherein said inverse-freezing material comprises a smallmolecule selected from the group consisting of:4-cyano-4′-octyloxybiphenyl liquid crystal, 4-methylpyridine (4MP),alpha cyclodextrin, nicotine, or any combination thereof.
 9. The articleof claim 7, wherein said inverse-freezing material comprises thecellulose derivative.
 10. The article of claim 9, wherein said cellulosederivative comprises an alkyl cellulose.
 11. The article of claim 10,wherein said alkyl cellulose comprises hydroxypropylcellulose, methylcellulose, or a combination thereof.
 12. The article of claim 1, whereinsaid interior layer further comprises an additive selected from thegroup consisting of: polymer, rubber, polystyrene, polyethylene,polypropylene, a polyvinyl, graphite, polysaccharide, polyvinyl alcohol(PVA), alginic acid, poly(methyl methacrylate) (PMMA), polyvinylpyrrolidone, polythiophene, polylactic acid, polysuccinimide, acrylicpolymer, methacrylic acid polymers, polyamines, polyamides, peptides,polyesters, polyurethanes, a biomolecule or bio-sourced material,corn-flour (starch), starch derivatives, polyamine, Flubber or aderivative thereof, diamond, graphene, ceramics, metals, metalloids, andany composition thereof, boron carbide (B4C), boron nitride, siliconcarbide, tungsten carbide, aluminum, alumina, silicon, silica andinorganic silicates, alkali and earth-alkali hydroxides and oxides, orany combination or mixture thereof.
 13. The article of claim 1, whereinsaid interior layer is in a form of a composition selected from liquid,solid, semi-solid and gel.
 14. The article of claim 13, wherein aconcentration of said inverse freezing material within said compositionis at least 3%.
 15. The article of claim 1, wherein said interior layeris in a form of a sealed confinement.
 16. The article of claim 1,wherein said energy is a mechanical energy.